FC Barcelona saved themselves with a 1-1 draw thanks to a 93rd minute equaliser from Rivaldo at Leeds United.
The English club were set to go through to the last sixteen after a convincing performance when Rivaldo scored in extra time to peg back Leeds.
Alan Smith decided to end the game by throwing punches at Barca defenders as Leeds let their frustration show and the English side now need to avoid defeat at Milan to push out Bbarcelona.
The Barcelona club are unlikely to see the chance of UEFA Cup games as any compensation for Champions League failure and coach Llorenc Serra Ferrer could be sacked by president Joan Gaspart.
Gaspart backed the coach after a poor start to the league season and Barca's league campaign has improved recently but Gaspart is targeting the Champions League for success and with Real Madrid already through to the second round as reigning champions, the pressure on Serra Ferrer will mount.
Leeds were put in total control of the first half by a fourth minute error from goalkeeper Richard Dutruel.
A speculative looping free kick by Lee Bowyer out on the left wing saw Dutruel advance from goal and allow it to fly over him into the net to shock Barca.
Their defence was likely to come under great pressure at Leeds and Dutch centre back Frank De Boer continues to be frozen out and did not start.
Barca had to attack from the start but it took until the 22nd minute to get off a shot when Rivaldo hit a snap shot that goalkeeper Paul Robinson blocked well.
A Xavi free kick was blocked well by Lee Bowyer in the 32nd minute but Mark Viduka almost scored a second goal for Leeds when he glanced a corner towards goal from close range with his head.
A first half of few chances was dominated by the hard running of the Leeds side and their players deservedly celebrated at the end of the first half when they ran to congratulate Robinson for a superb innjury time save.
Rivaldo fired a low free kick under the defensive wall which Robinson saw late and saved to keep Leeds in control.
Barca got the majority of possession at the start of the second half but Leeds always threatened on the break with Mark Viduka proving a great outlet for the Leeds defence with some excellent runs into the Barcelona back areas.
Gradually though Barca took control of the whole game and Leeds could not get into the opposition half.
It was then up to goalkeeper Paul Robinson to produce one of the best displays of the season so far. Robinson beat away a close range header from Alfonso after good work from Luis Enrique to set up two even better saves.
Rivaldo hit a free kick in the 65th minute which Robinson saved and then the young 'keeper dived low to his near post to beat away another free kick from the Brazilian star in the 68th minute.
Xavi managed to avoid Robinson but his shot went just over the bar in the 72nd minute.
Barca thought they had scored just after this but Rivaldo's tap in was ruled offside. He was not offside but substitute Dani was ruled to be interfering with play.
A succession of corners ended deep in injury time when substitute Gerard Lopez struck the post from close range and Rivaldo was in range of the rebound to tap in.
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