Lionel Messi was sent off for the first time in his Barcelona career as his side were beaten 3-2 after extra time by Athletic Bilbao in the Spanish Super Cup final.
The Argentinian was pulled up by VAR for lashing out at Asier Villalibre in the final minutes of the additional 30, after Inaki Williams had netted the decisive goal in the fourth.
Antoine Griezmann had opened the scoring for Barcelona in the 40th minute, slotting past Bilbao goalkeeper Unai Simon to give his side the lead, only for Oscar De Marcos to find the leveller just two minutes later.
Barca looked to have secured victory when Griezmann turned home his second goal of the game from seven yards out in the 77th minute, but Bilbao substitute Villalibre volleyed in a 90th-minute equaliser.
Williams curled the ball into the top corner to put Bilbao ahead for the first time in the game, before things went from bad to worse for Ronald Koeman's side as Messi saw red.
Arturo Vidal scored in a 2-0 win over his former club Juventus to move Inter Milan level on points with city rivals AC Milan at the top of Serie A.
In the Derby d'Italia, Cristiano Ronaldo struggled to make his mark as Vidal put the home side ahead in the 13th minute with a header past former Arsenal goalkeeper Wojciech Szczesny.
Just after the interval, Nicolo Barella put the ball in the top corner to double his side's lead and secure an important three points for Inter.
Napoli thrashed Fiorentina 6-0 in a dominant display at the Stadio Diego Armando Maradona.
Lorenzo Insigne opened the scoring after five minutes, before the second and third came in quick succession in the 37th and 38th minutes, with Diego Demme and Hirving Lozano adding their names to the scoresheet.
Piotr Zielinski added a fourth, before Insigne converted a penalty in the 72nd minute and Matteo Politano capped off the scoring one minute from time.
Elsewhere, Crotone comfortably beat Benevento 4-1, while Sassuolo drew 1-1 with Parma and there were no goals in the clash between Atalanta and Genoa.
Robert Lewandowski netted his 21st goal of the season as Bayern Munich beat Freiburg 2-1.
The Poland striker has racked up his tally in the first 16 games of the season, breaking a Bundesliga record when he struck in the seventh minute.
Nils Petersen levelled with a header in the second half, before Thomas Muller struck the winner in the 74th minute to claim all three points for Bayern.
Also in the Bundesliga, Luka Jovic made a triumphant return to Eintracht Frankfurt as he netted two late goals to earn a 3-1 win over Schalke.
Jovic is back at the club on loan from Real Madrid having enjoyed an impressive previous loan spell with the Bundesliga club during his time with Benfica.
In Ligue 1, Lille moved to level on points with league leaders Paris St Germain after coming from behind to secure a 2-1 win over Reims.
Lyon missed an opportunity to take top spot after they fell to a 1-0 defeat at home to Metz.
Bordeaux won 3-0 at Nice, while Nantes and Lens played out a 1-1 draw and a late Clement Grenier penalty gave Rennes all three points in a 2-1 win at Brest.