Piotr Trochowski put Sevilla ahead after 26 minutes and when Alvaro Negredo doubled the advantage after the break it looked as though the Andalusians would achieve a double over the top two, having beaten Real a fortnight ago.
However, Barca fought back with Cesc Fabregas reducing the arrears after 53 minutes and then the talking point was the dismissal of Gary Medel for an apparent headbutt on Fabregas which led to him being red-carded with 18 minutes to go.
Barca pressed forward and it was Fabregras who equalised with a minute to go before substitute David Villa got the winner in the fourth minute of injury time.
Barca coach Tito Vilanova felt it was right to send off Medel.
“If a player goes towards another and hits them in the head then the referee does the right thing to apply the law. That is a red card here or anywhere. It is difficult to referee and easy to make mistakes but not in this case,” he said.
Sevilla coach Jose Miguel Gonzalez ‘Michel’, who was sent to the stands in closing stages for complaining too vociferously, refused to get drawn into questions about Medel’s dismissal.
“Sometimes things are just crystal clear but still rules are about interpretation and I never talk about referees,” he said.
“My players were excellent against an excellent rival. I won’t say it was an unjust result but it was frustrating and leaves a bitter taste in my mouth.”
The pressure is now very much on Real Madrid who face Deportivo La Coruna on Sunday before they then go head-to-head with Barcelona in the first El Clasico of the season in the league next weekend.
Barca started stronger and Pedro Rodriguez fired over in the opening minutes.
Goalkeeper Andres Palop then got down well to stop Lionel Messi inside the area after 13 minutes.
Sevilla’s Ivan Rakitic had a tame shot from the edge of the area before, on another breakaway, Trochowski gave the home side the lead.
The ball came to him after Javier Mascherano tried to clear the danger and from the left-hand side of the area the Sevilla man slotted the ball into the corner.
Straight after the restart Sevilla got their second goal after Sergio Busquets gave the ball away in midfield. Medel found Negredo who clipped the ball over the keeper for a fine finish.
Barca went close through Pedro Rodriguez before Fabregas pulled a goal back with a shot from the edge of the area.
Medel was controversially dismissed for a headbutt on Fabregas and then, in the closing minutes, it was the former Arsenal man who ran through to beat Palop.
There was still time three minutes into injury time for Villa to latch onto a Messi pass for the winner.
Malaga maintained their unbeaten start as they cruised to a 4-0 victory over Real Betis with the game turning on an early penalty and the sending off of goalkeeper Casto Espinosa.
Casto was red-carded for a foul on Eliseu Pereira and after Joaquin Sanchez converted the penalty, Malaga never looked back.
They had a series of chances with Ignacio Camacho hitting the post with a header and then Javier Saviola slotted home the second after 28 minutes following an exchange with Francisco Portillo.
Midway through the second half Antonio Amaya put the ball through his own net as he intercepted a Nacho Monreal cross and then Isco Alarcon finished clinically to add to Betis’ misery.
Elsewhere Valencia beat Zaragoza 2-0 and Real Sociedad also came out on top 2-0 against Athletic Bilbao.