Barca also lost record signing Ousmane Dembele with a hamstring injury which will sideline him for three or four months.
Valverde made a brave change at the break when he replaced Andres Iniesta with Denis Suarez at the break, and Suarez rewarded him by scoring the equalizer on the hour. This was before Barca's third substitute, Paulinho, netted the winning goal with five minutes left to play.
Atletico Madrid inaugurated their Wanda Metropolitan Stadium with a 1-0 win over Malaga thanks to a 61st minute goal from Antoine Griezmann following good work from Angel Correa.
The game ended with celebrations on the pitch for Atletico, but Malaga are bottom of the table with zero points from their first four matches of the season.
Alaves are also pointless after their four matches following their defeat 3-0 at home to Villarreal.
Cedric Bakambu scored twice and Carlos Bacca netted the third as the visitors enjoyed a comfortable win against a side which looks to be the shadow of the one which reached last season's King's Cup final and Alaves coach Luis Zubeldia later became the first managerial casualty in La Liga.
Las Palmas took advantage of a tired Athletic Club Bilbao, who had played in Berlin on Thursday to win 1-0 at home thanks to an 87th minute goal from former Chelsea striker Loric Remy to end Athletic's unbeaten start to the season.
Levante and Valencia remain unbeaten at the start of the season as they drew 1-1 in the Valencia city derby.
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