Getafe stunned local rivals Real Madrid while Lionel Messi secures a late victory for Barcelona, while Sampdoria return to Serie A in style with a 1-0 win over AC Milan.
European football round-up: Madrid and Milan suffer shock defeats
Real Madrid's disappointing start to the season continued tonight as they suffered a shock 2-1 defeat at local rivals Getafe despite leading at half-time.
Gonzalo Higuain put Madrid ahead in the 27th minute, but Getafe hit back in the second half to stun their star-studded opponents with goals from Juan Valera and Abdelaziz Barrada.
There were no such worries for Barcelona, thanks to Lionel Messi who scored twice in the last 15 minutes as his side survived a scare against 10-man Osasuna to continue their winning start to the season.
Joseba Llorente volleyed the home side in front in the 17th minute, before Nino came close to doubling Osasuna's lead.
Messi, as has often been the case, was the spark behind the comeback, and he drew the teams level in the 75th minute when he stabbed home Alexis Sanchez's pass to finish off a move he himself had started with a trademark darting run.
Osasuna were aggrieved that goal was allowed to stand after Alexis had appeared to be offside when he received the ball earlier in the move, and the home side's veteran midfielder Patxi Punal was handed his marching orders for taking his protests too far.
Barca quickly made the most of their man advantage as, in the 80th minute, summer signing Jordi Alba picked out Messi near the edge of the area and the Argentina superstar rolled a low shot into the far corner for the match-winner.
Sevilla came from behind with 10 men to claim a valuable point from a 1-1 draw in the first Andalusian derby of the season at Granada.
The visitors had goalkeeper Diego Lopez sent off just after the half-hour mark when he upended Antonio Floro Flores inside the area and, despite his replacement Andres Palop saving Guillherme Siqueira's penalty, Mikel Rico rattled in the rebound to give Granada the lead.
However, Alvaro Negredo headed home a minute before the break to bring Sevilla level and Michel's side defended relatively comfortably until a late flurry saw Darwin Marchis head two golden opportunities over and Floro Flores hit the crossbar.
Serie A newcomers Pescara were given a less-than-friendly welcome to top flight football after going down 3-0 to Inter Milan.
Wesley Sneijder got Inter up and running with 17 minutes gone, before Diego Milito then caught them cold with a second two minutes later.
Phillipe Coutinho wrapped things up for Andrea Stramaccioni's men nine minutes from time.
Sampdoria made a winning return to Serie A with a shock 1-0 victory at AC Milan.
Andrea Costa scored the only goal of the game just before the hour mark and, despite Milan hitting the woodwork twice, supporters made clear their frustration at the final whistle.
Lazio also opened their campaign with a 1-0 victory at Atalanta, courtesy of Anderson Hernanes' 18th-minute goal, while Napoli's bid to improve on last term's top-five finish got off to a flying start with a 3-0 victory in Palermo, with Marek Hamsik, Christian Maggio and Edinson Cavani all on target.
Chievo kicked off the new season with a workmanlike 2-0 victory over Bologna.
Talismanic skipper Sergio Pellissier opened the scoring for the hosts in the second half and Rinaldo Cruzado doubled the lead 11 minutes from full-time.
Second-half goals from Alexander Merkel and Ciro Immobile were enough to earn Genoa a routine 2-0 win over Cagliari.
Cristobal Jorquera missed a 17th-minute penalty for the hosts, but Merkel got things going six minutes after the break and Immobile finished things off with five minutes left.
Zdenek Zemen's return to Serie A as coach of Roma was not a winning one as his men played out a 2-2 draw with Catania.
Giovanni Marchese and Alejandro Gomez twice put the visitors in front but the Giallorossi responded with goals from Pablo Osvaldo and Nico Lopez.
Siena, who are trying to overturn a six-point deduction for their part in a match-fixing scandal, could only manage a goalless draw against newly promoted Torino.
Marseille maintained their 100% start to the season with a 1-0 win over reigning champions Montpellier to move to the top of Ligue 1.
Andre-Pierre Gignac struck the winning goal in the 77th minute, capitalising on an error in the Montpellier backline, as OM moved two points clear at the top of the table with three wins from three under new boss Elie Baup.
Big-spending Paris St Germain remained frustrated in pursuit of their first victory as they were held to their third draw in as many games - a goalless stalemate at home to Bordeaux, who dropped points for the first time this season.
St Etienne picked up their first win of the campaign with a 4-0 demolition of Brest.
Pierre-Emerick Aubameyang bagged a goal in either half for the victors, while Romain Hamouma (29) and Josuha Guilavogui (61) were also on the scoresheet.
Teenage substitute Thomas Reilly grabbed a last-gasp equaliser for St Mirren to prevent Motherwell from going top of the Premier League.
Michael Higdon had opened the scoring for Motherwell inside the first two minutes, after an error by Lee Mair, but Stuart McCall's side failed to extend their lead at Fir Park.
And with seconds remaining, Motherwell goalkeeper Darren Randolph's save from a Steven Thompson shot was bundled over the line by 17-year-old Reilly.
Hearts missed the chance of an injury time winner against Aberdeen after Andrew Driver's shot came off the post at Pittodrie to leave both sides goalless.
And Berwick Rangers were unlucky not to claim another upset win over former giants Rangers in Division 3. Andy Little opened the scoring for Rangers just before half time, before Berwick substitute Fraser McLaren scored the equaliser in 62 minutes.
FC Twente continued their 100% start to the Eredivisie season with a 3-1 win at NEC Nijmegen.
First-half goals from Luc Castaignos, Dmitri Bulykin and a Leroy Fer penalty did the damage for the visitors, with Evander Sno's 77th-minute strike providing scant consolation for NEC.
The result moved Steve McClaren's side onto nine points from three games - two points ahead of champions Ajax, Vitesse Arnhem, RKC Waalwijk and Feyenoord.
Jonathan Reis' brace was enough for Vitesse to sink Willem II 2-0 in Tilburg, while Feyenoord were 2-1 winners at Heracles Almelo.
Darryl Janmaat and Lex Immers scored at either end of the first half to put the Rotterdammers ahead. Lerin Duarte's goal seven minutes after the interval restored hope for the hosts but they could not find an equaliser.
PSV Eindhoven grabbed their second win of the season with a 3-1 win over FC Groningen at the Euroborg.
Atiba Hutchinson set the visitors on their way seven minutes before half-time and second-half goals from Dries Mertens and substitute Memphis Depay put the result beyond doubt before Mitchell Schet reduced the deficit a minute from time.
AZ Alkmaar and Heerenveen had to settle for a point apiece after a goalless draw at the AFAS Stadion.