Real Madrid all but handed the La Liga title to Barcelona as they let in two goals to collapse in the final 20 minutes at home to Villarreal.
Samuel Chukwueze scored twice, the second a brilliant effort 10 minutes from time after Jose Morales had levelled, as Real threw away the lead to go down 3-2 after Vinicius Junior's goal just after half-time seemed to have them in sight of victory.
Elsewhere, Real Sociedad strengthened their grip on fourth place with a 2-1 victory over Getafe, Athletic Bilbao kept their European hopes alive with a win at Espanyol and Osasuna beat bottom side Elche.
Bayern Munich stayed two points clear at the top of the Bundesliga as Matthijs de Ligt's fine second-half drive proved enough for a 1-0 win away at Freiburg.
The Netherlands international fired into the top corner from 25 yards shortly after the break to hand Thomas Tuchel his second victory in his first two league games and maintain their lead over second-place Borussia Dortmund.
Union Berlin had the chance to unseat Dortmund as the main challengers to Bayern if they could get the better of Edin Terzic's side at Signal Iduna Park, but fell to a 2-1 defeat thanks to a winning goal from 18-year-old substitute Youssoufa Moukoko.
Earlier, Kevin Behrens levelled for the Bundesliga's surprise package as they looked to keep their bid for a first-ever Champions League place on track, after Donyell Malen had given the home side the lead.
Bayer Leverkusen beat Frankfurt 3-1 to leapfrog the Europa League holders into the European places, whilst Mainz and Werder Bremen drew 2-2. Augsburg went down 3-1 at home to Koln and Leipzig were 1-0 winners against Hertha Berlin.
In Serie A, Roma took control in the race to finish in the top four, Jose Mourinho's side winning 1-0 away at Torino to move up to third courtesy of Paulo Dybala's early penalty.
Elsewhere in the race for the Champions League, Atalanta's hopes took a hit as they lost 2-0 at home to Bologna with goals in the second half from Nicola Sansone and Riccardo Orsolini.
Napoli's runaway lead at the top was snipped back to 16 points following Friday's win at Lecce, as Lazio won 2-1 against Juventus to ensure Luciano Spalletti's side are still three wins at most from the title.
Cremonese won for just the second time all season to move off the foot of the table, Leonardo Sernicola scoring five minutes into added time to beat Sampdoria after Luca Lochoshvili had levelled in the 85th minute.
Defeat dropped their opponents to the foot of the table, though both teams look doomed to relegation.
Verona's hopes of beating the drop were handed a huge boost as they came from behind to beat Sassuolo 2-1 at home, whilst Spezia drew with Fiorentina to leave the gap at four points in the relegation stakes. Udinese and Monza played out an entertaining 2-2 draw.
Lionel Messi scored his 14th league goal of the season as Paris St Germain eased to a 2-0 win away at Nice, whilst elsewhere in Ligue 1 bottom side Angers beat Lille 1-0.
