Valencia came from behind to beat Barcelona 3-1 on the final day of the LaLiga season at Mestalla, though it was not enough to secure European qualification.
Robert Lewandowski marked his expected final Barcelona appearance with a goal, firing the champions ahead just after the hour mark to bring up his 119th goal in four seasons with the club.
But the lead lasted only five minutes as Javi Guerra levelled with a fine finish, and Valencia were ahead four minutes later when Guerra's shot was blocked and fell to Luis Rioja, who fired a left-footed shot past Wojciech Szczesny.
The hosts thought they had a penalty when Marc Bernal brought down Jesús Vázquez, but a VAR check showed the incident occurred outside the box.
The third goal arrived deep into stoppage time when Guido Rodríguez found the net from outside the box to wrap up the victory.
Valencia needed other results to go their way to qualify for Europe, but Getafe's win over Osasuna and Rayo Vallecano's victory at Alavés meant they remained out of the European places despite the win.