A stunning late double from Argentine star Maxi Rodriguez gave Atletico Madrid a dramatic 2-1 win over Sevilla.
The Uefa Cup holders had been top of La Liga going into the weekend action but Real Madrid went above them after their win at Real Betis on Saturday.
However, Sevilla missed the chance to go back top after losing out at The Vicente Calderon.
Renato had put Sevilla ahead just before the interval and that looked to be enough to seal victory but then Maxi (pictured) struck in the 85th and 88th minute to give Atletico a memorable win.
Sevilla's task had been made all the more difficult as they actually finished the game with nine men as both Julien Escude and Javi Navarro saw red before Maxi's double.
The game of the weekend in Spain was Valencia's trip to Barcelona. Following Sevilla's failure to win - both teams were in prime position to take advantage.
However, neither side could work victory - as they played out an entertaining 1-1 draw at Camp Nou.
Valencia shocked the home side as they took the lead with a wonderful piece of football. Vicente played Miguel in down the right flank and the Portuguese full back crossed to the back post the ubiquitous David Villa to slide the ball home.
Barcelona coach Frank Rijkaard reacted at the interval by bringing on Anders Iniesta for Edmilson and the move paid dividends just minutes later as the Spanish international slotted home after some wonderful link-up play between Ronaldinho and Samuel Eto'o.
Both sides had chances late on but it was Barca who could have snatch victory but Santiago Canizares held firm in the Valencia goal to seal a share of the spoils for Los Che.
However, the point was enough for Barcelona to claim top spot ahead of Real Madrid and goal-difference, with Valencia also on ten points but in third.
Deportivo La Coruna dropped back to sixth in La Liga after going down 2-0 to Levante.
French international Olivier Kapo was the hero for the home side as he bagged a goal in either half (18 & 76). The game was marred by a red card for both sides with Mathieu Berson (54) and Fabian Estoyanoff (80) both going off.
Racing Santander claimed there first point of the new season with a 2-2 draw at Gimnastic de Tarragona.
The newly promoted side were twice ahead through David Cuellar (38) and Javier Portillo (66), but each time Serbian Nikola Zigic pounced to claim a share of the spoils - with his second coming deep in injury time.
Athletic Bilbao made sure they did not drop to the foot of the table as they claimed a 0-0 draw at Getafe. There were further dismissals at The Alfonso Perez as Bilbao had two red cards and Getafe one.
Aritz Aduritz (42) and Ander Murillo (86) went for the visitors while Cosmin Contra (51) was dismissed for the home side.
Real Zaragoza missed the chance to move into the top six as they went down 3-2 at Villarreal.
Pablo Aimar gave Real the lead after 22 minutes but The Yellow Submarines came out fighting in the second half as Ruben Cani (49), Diego Forlan (59) and Juan Roman Riquelme (79 pen) scored.
Gabriel Milito was then dismissed for Zaragoza but they still managed a consolation through Gerard Pique.
Celta Vigo were upset at home as Osasuna claimed a 2-0 win at The Balaidos as Valdo (35) and Juanfran (92) both scored. The home side were reduced to ten men also as Lopez Angel saw red.
Recreativo de Huelva claimed an impressive 3-2 win at Real Sociedad. Antonio Sanchez de la Calle (39 & 53) struck twice for the visitors, but Real pulled it back level as Garcia Uranga (65) Alvaro Novo (77 pen).
However, Recreativo secured the win as Liverpool loanee Florent Sinama Pongolle fired home in injury time.
Real Mallorca collected their first win of the season as Maxi Lopez (78) fired home the only goal of the game against Espanyol - who had Albert Riera sent off late on.
Click below for match summaries:
Atletico Madrid 2-1 Sevilla
Barcelona 1-1 Valencia
Celta Vigo 0-2 Osasuna
Getafe 0-0 Athletic Bilbao
Gimnastic 2-2 Racing Santander
Levante 2-0 Deportivo La Coruna
Real Mallorca 1-0 Espanyol
Real Sociedad 2-3 Recreativo Huelva
Villarreal 3-2 Real Zaragoza