Renato headed home Frederic Kanoute's right-wing cross to decide a pulsating encounter that saw Madrid reduced to 10 men when Arjen Robben was sent off on 77 minutes.
The result lifted Sevilla above Real Madrid and into fourth place in La Liga, with Bernd Schuster's team dropping to fifth - nine points behind leaders Barcelona, who they face next week.
Sevilla went ahead on six minutes when Madrid goalkeeper Iker Casillas misjudged a right-wing cross and presented Adriano Correia with a simple tap-in.
But Madrid levelled on 19 minutes, when Raul stooped to head home Guti's free-kick from the right and claim his 302nd goal for Madrid.
Sevilla regained the lead just three minutes later, however, when Romaric headed home Renato's fine cross from the right.
To the astonishment of the home fans, Sevilla went further ahead on 39 minutes. Madrid were caught napping in their own penalty area and Kanoute pounced to calmly slot home.
The second half saw Madrid finally begin to play to their potential. Gonzalo Higuain crashed a superb shot past Andres Palop on 67 minutes to make it 3-2, then Fernando Gago headed home a Guti free-kick to complete a remarkable comeback.
Madrid almost went ahead when Higuain went round Palop and struck the bar with his shot. But the Madrid players thought the goalkeeper had fouled the Argentine and Robben protested so strongly he earned himself a second yellow card and his marching orders.
Sevilla sensed their opportunity against the 10 men of Madrid and when Kanoute found himself in acres of space on the right flank he took his time before picking out the unmarked Renato to head home the winner.
DEPORTIVO CORUNA 2-0 MALAGA
Malaga had Depor on the ropes until Inaki Goitia let Angel Lafita's free kick slip through his hands in the 65th minute.
Mexico striker Omar Bravo theatrically went to ground for a penalty soon after, and secured the win himself from the spot.
NUMANCIA 2-1 ALMERIA
Under-pressure Almeria coach Gonzalo Arconada had an unhappy return to his former club despite Argentine forward Esteban Solari giving the visitors an early lead from the penalty spot.
Javier del Pino levelled after a counter-attack in the 19th minute and Asier Goiria was offside when he netted the winner in the 52nd. Numancia had Jose Barkero sent off in the 68th.
OSASUNA 3-3 REAL VALLADOLID
Osasuna dominated and Portuguese striker Dady headed them into the lead after 17 minutes. Iran midfielder Javad Nekonam doubled the lead with a volley before the break and Dady made it 3-0 in the 57th.
Valladolid's fightback started when Swedish striker Henok Goitom scored from close range on the hour, and then Miguel Flano headed into his own net at a free kick. Bartholomew Ogbeche headed the equaliser from another free kick in the 85th.
RACING SANTANDER 1-1 ATHLETIC BILBAO
Bilbao's Fran Yeste broke the deadlock in the north-coast derby with a deflected free kick in the 49th minute, but they had Pablo Orbaiz sent off in the 77th.
Gonzalo Colsa's cross-cum-shot in the 83rd caught out Gorka Iraizoz as it drifted over him at the back post. Bilbao's Fernando Amorebieta missed an open goal in the last minute.
REAL BETIS 1-1 ESPANYOL
Espanyol hit the woodwork twice in the first half but Betis took the lead when Cameroon midfielder Achille Emana scored his fifth goal in as many games in the 57th minute.
Substitute Ferran Corominas earned a point for new Espanyol coach Mane with a fine piece of skill in the 71st, ending a run of four straight defeats for the visitors.
REAL MALLORCA 2-3 RECREATIVO HUELVA
David Navarro's diving header put Mallorca ahead in the 16th minute but Argentine Marco Ruben's neat finish levelled the scores nine minutes later.
Jurado put Mallorca back in front on a swift break only for Adrian Colunga to equalise again in the 43rd with a well-worked move. Javi Fuego's long-range shot secured new Recre coach Lucas Alcaraz his first win since taking over in early October.
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