The curse of the San Siro continued to blight AC Milan's season, while Jose Mourinho watched his side go down 1-0 to Sevilla in the worst start to a season for Madrid in a decade.
European football round-up: Nightmare start for Real Madrid continues
Lionel Messi climbed off the bench to score twice while fellow substitute David Villa was again on the mark as Barcelona continued their 100% start to the new Primera Division season with a 4-1 victory over Getafe.
Adriano capitalised on good work by Cesc Fabregas to notch a 32nd-minute opener before the visitors added three more goals in the final 16 minutes to seal their fourth win in four league outings.
Messi doubled the lead from the penalty spot before the Argentina ace made it 3-0 four minutes later. Getafe pulled a goal back through Pablo Sarabia's deflected strike but Villa had the final word with a brilliant piece of finishing in stoppage time to complete the scoring.
Meanwhile Real Madrid sank to a successive defeat tonight, losing 1-0 at Sevilla to fall eight points behind Barcelona in their worst La Liga start in a decade.
Piotr Trochowski lashed home after 69 seconds and Madrid could not find a response, instead counting themselves lucky that not one but two of their players avoided red cards that could easily have been shown to Gonzalo Higuain and Angel Di Maria in separate incidents.
Valencia earned their first league victory after easing past newly-promoted Celta Vigo 2-1 at the Mestalla.
Sofiane Feghouli gave Valencia an early lead and although Celta equalised soon after through Michael Krohn-Delhi, the hosts claimed the points thanks to Aly Cissokho's 50th-minute winner.
Malaga maintained their unbeaten start to the league campaign with a comfortable 3-1 win over Levante thanks to goals from Javier Saviola, Joaquin and Francisco Portillo.
Saviola deservedly put the hosts in front after 26 minutes with a simple finish from Isco's fine through ball, but Levante were level a minute after half-time when Michel thundered in from outside the area.
However, Malaga's lead was restored 12 minutes later when Saviola's cute pass found Joaquin free inside the area and his calm finish gave Gustavo Munua no chance.
And, despite losing Sergio Sanchez to a second yellow card three minutes from time, Portillo sealed all three points with a controlled volley in the last action of the match.
The curse of the San Siro continued for AC Milan as they lost 1-0 to Atalanta - meaning neither Milan nor Inter have won at their home stadium in five attempts this season.
Luca Cigarini scored the only goal of the game in the 64th minute as their tactical control of the game left Milan without a cutting edge. 0
Palermo and Cagliari shared the points in a 1-1 draw following maiden Serie A goals from Egidio Arevalo Rios and Marco Sau
The Uruguayan scored five minutes before half-time to give Palermo the lead, but Sau's reply two minutes from the end meant both sides failed to get the win they were looking for.
The 1-1 draw leaves both island clubs still searching for their first wins of the season
Sochaux picked up their first Ligue 1 victory of the season after beating St Etienne at the Stade Geoffrey-Guichard.
Thierry Doubai's overhead kick after 75 minutes won the game for the visitors, after the hosts had to play 80 minutes with 10 men following Jonathan Brison's red card.
Evian also picked up their first win of the campaign, with a 3-0 showing against Bastia.
Pascal Dupraz`s side put on a show at the Parc des Sports, opening the scoring through Cedric Barbosa, with the same player putting the cap on it with 13 minutes left after Yannick Sagbo had netted a second.
There was also a first success for Nice who got the better of Brest 4-2 after a dominant second-half display.
A lacklustre first half was soon forgotten once the second period began, with Camel Meriem, Nemanja Pejcinovic, Eric Bautheac and Valentin Eysseric all finding the target for the home side.
Jonathan Ayite and Paul Baysse replied for Brest but the damage had already been done by that stage.
Troyes' search for a first win of the season will go on after they played out a 1-1 draw with Lille.
Things could have been worse for the hosts, who trailed for much of the match to Dimitri Payet's first-half strike.
However, substitute Sebastian Grax came to the rescue in the final few minutes to secure only the second point of the campaign for Troyes.
Elsewhere, Bordeaux boss Francis Gillot's call for his side to take more of their chances fell on deaf ears as they were held to a goalless draw at Valenciennes.
FC Twente continued their stunning start to the Eredivisie season with a 6-2 thrashing of Willem II in Tilburg.
Twente have yet to drop any points this campaign and have scored 15 times in five matches, conceding just four goals.
The scoring began after 39 minutes when Felipe Gutierrez made the most of a Roberto Rosales pass to tap home, before Luc Castaignos pounced on a poor defensive pass to double the lead two minutes later.
Gutierrez then teed up Robbert Schilder for his first of the match - and Twente's third - after 53 minutes, before Marc Hocher's 71st-minute reply gave Willem II a brief glimmer of hope. That was quickly extinguished, however, as Schilder and Willem Janssen scored two goals in as many minutes to effectively end the contest.
Jeroen Lumu's strike for the home side six minutes from time was little more than a consolation and their miserable evening was completed when Philipp Haastrup put through his own net in the dying minutes.
Ajax climbed up to second with a routine 2-0 victory over RKC Waalwijk.
The defending champions went ahead after 52 minutes when Lasse Schone benefited from a pass by Danish compatriot Christian Eriksen to sweep the ball home right footed.
Jody Lukoki then added a fortunate second after 68 minutes. The winger failed to get much power behind his shot but RKC goalkeeper Jeroen Zoet still let the effort roll between his legs and into the net.
Feyenoord were also 2-0 winners over Zwolle, a result which saw them move into the top four.
Graziano Pelle fired home the opening goal at the start of the second half with a strike which took a helpful deflection off Joost Broerse, before Lex Immers scored from the spot after 73 minutes.
Heerenveen's disappointing start to the campaign continued as they succumbed 3-1 at home to 10-man ADO Den Haag.
Rydell Poepon fired home the opener from Tjaronn Chery's pass after 20 minutes and Jens Toornstra scored the second goal four minutes later, tapping home the rebound after Kevin Jansen's curling strike had come back off the post.
Chery added a third after 28 minutes, pinching the ball from Youssef El Akchaoui and sliding home a shot. Jeffrey Gouweleeuw pulled a goal back in the 53rd minute after the visitors failed to clear a corner kick.
Uche Nwofor scored a brace as VVV-Venlo came from two goals down to claim a 2-2 draw against NEC Nijmegen.
The hosts trailed after just two minutes when Michel Breuer headed home a free kick from Ryan Koolwijk, and that deficit was doubled 10 minutes into the second half with another header, this time from Melvin Platje.
But Nwofor pulled a goal back from close range after 67 minutes and made sure the points were shared nine minutes later with a header of his own.
Champions Celtic were sent a message that their road to retaining the Scottish Premier League title will not be easy after suffering a 2-1 defeat in Perth to St Johnstone.
Kris Commons opened the scoring for Neil Lennon's side after just four minutes, but Gregory Tade turned onto a Rowan Vine pass to drive pass Fraser Forster from the edge of the box.
Celtic felt they had been denied a penalty after a challenge of Commons, but with ten minutes remaining, Vine picked up on a Nigel Hasselbaink ball to step past Thomas Rogne and curl the ball into the net.
Motherwell remain top of the SPL after a 2-1 win at Dundee. The league newcomers took the lead in the 20th minute when Colin Nish bulleted home a powerful header, but Michael Higdon equalised with 15 minutes remaining after turning home a Henrik Ojamaa cross.
Higdon made it two with five minutes left, lashing home a Tom Hateley corner to snatch victory.
Hibernian continued their early progress with a 2-1 win over Kilmarnock. Leigh Griffiths scoring straight from a corner for the first, and with a penalty on the stroke of half time for his second, bookending an equaliser by Danny Racchi.
St Mirren recorded their first win of the season with goals from Jim Goodwin and Lewis Guy to take a surprise 2-0 win over Hearts.
Inverness Caledonian Thistle drew 1-1 with Aberdeen after Richie Foran's second-half penalty was cancelled out by a late goal from teenager Cammy Smith.
Defending Bundesliga champions Borussia Dortmund ran out 3-0 victors over Bayer Leverkusen to extend their unbeaten record to 31 matches and move up to third in the table.
Mats Hummels put Jurgen Klopp's men in front in the 29th minute before Jakub Blaszczykowski added a second 10 minutes later. Robert Lewandowski wrapped up victory in a one-sided encounter in the 78th minute.
Bayern Munich maintained their perfect start to the season with a convincing 3-1 victory over Mainz at the Allianz Arena.
Mario Mandzukic and Bastian Schweinsteiger gave the hosts a two-goal lead within the first 13 minutes, but Adam Szalai reduced the arrears from the penalty spot in the 59th minute.
However, Toni Kroos wrapped up victory with practically the last touch of the game as Bayern made it three wins out of three in the league.
Hiroshi Kiyotake scored one and set up two more as Nurnberg shrugged off a Borussia Monchengladbach fightback to win 3-2.
The Japan international sent in the free kick from which Timm Klose scored in the 17th minute and then a corner for Timmy Simons to head in after 25 minutes as Nurnberg took a 2-0 lead.
Luuk de Jong halved the deficit in the 45th minute and Granit Xhaka equalised after 53 minutes, but Kiyotake struck the winner in the 55th minute.
Szabolcs Huszti scored his second goal of the game and was sent off for over-celebrating two minutes into stoppage-time as 10-man Hannover clinched a thrilling 3-2 victory at home over Werder Bremen.
Huszti scored the opener in the sixth minute and teed up Leon Andreasen's goal that gave Hannover a 2-0 lead after 10 minutes.
Aaron Hunt converted from the spot to cut the deficit to 2-1 in the 26th minute, and Kevin De Bruyne equalised in the 74th minute before Huszti scored a late winner - then was shown two yellow cards for celebrating.
Schalke extended their unbeaten start to the season with a 2-0 victory at Greuther Furth, who lost for the second time in a row at home.
Julian Draxler put the Royal Blues in front early in the second half with a stunning effort from distance and Lewis Holtby added the second in the dying stages of the match.
Stuttgart picked up their first point of the season in a lacklustre goalless draw against newly promoted Fortuna Düsseldorf, who are the only team in the Bundesliga not to have conceded a goal yet.
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