Frank Rijkaard's last game in charge of Barcelona at the Nou Camp ended in disappointment as Real Mallorca came from two goals down to claim a 3-2 win on Sunday.
The Dutchman, who is to be replaced by Josep Guardiola at the end of the season after a second trophy-less campaign, saw Dani Guiza snatch a stoppage-time winner to keep the visitors' UEFA Cup hopes alive.
Borja Valero and Pierre Webo had earlier struck in the space of three second-half minutes to bring Mallorca level after Thierry Henry and Samuel Eto'o had given the Catalans a two-goal lead.
Barca also had Edmilson sent off moments before Guiza's winner.
Atletico Madrid sealed the final Champions League spot after Diego Forlan scored in a 1-0 win over Deportivo La Coruna to ensure they will finish in fourth place.
Atletico are three points clear of Sevilla going into last game of season, but the capital club have a better head-to-head record.
Sevilla had to settle for UEFA Cup football despite winning 2-0 at local rivals Real Betis, Luis Fabiano and Federico Fazio were on target.
Garcia Arzu and Daniel Alves were both sent off in the 56th minute as the two sides ended with 10 men.
Racing Santander are now only one point ahead of Mallorca in the race for the final UEFA Cup place after they were held to a goalless draw at Athletic Bilbao.
Bilbao had substitute Francisco Yeste sent off in stoppage time, just 10 minutes after coming off the bench.
Real Zaragoza dropped into bottom three despite a late equaliser which snatched a 2-2 draw against champions Real Madrid.
A Sergio Garcia goal four minutes from time rescued a point after strikes from Ruud van Nistelrooy and Robinho had cancelled out Ricardo Oliveira's opener.
Recreativo Huelva and Osasuna moved a point clear of the drop zone after both recorded crucial wins.
First-half goals from Jesus Vasquez and Florent Sinama-Pongolle gave Recre a 2-0 win at Almeria, but they had to endure a second-half barrage after Iago Bouzon was sent off on the stroke of half-time.
Osasuna, who started the day in the bottom three, beat already-relegated Real Murcia 2-1 thanks to goals from Eduardo Dady and Torres Juanfran.
Substitute Gomez Abel grabbed a consolation for the visitors in stoppage time.
Elsewhere, David Villa bagged a hat-trick as Valencia romped to a 5-1 victory at basement boys Levante.
Juan Mata and Miguel Angulo also scored, while Jose Serrano had pulled a goal back to made it 2-1.
Second-placed Villarreal were 2-0 winners at home to Espanyol thanks to first-half goals from Javi Venta and Robert Pires.
The clash between Valladolid and Getafe ended goalless.
