Arne Slot’s side fell behind to Rodrigo Gomes’ strike in the closing stages at Molineux.
Mohamed Salah hauled Liverpool level with his first goal in 11 top-flight games dating back to November.
But Andre’s first goal for Wolves inflicted the latest humbling loss in a chastening season for Liverpool.
It was the first time the Premier League’s bottom club had beaten the reigning champions since Crystal Palace defeated Chelsea in 2017.
The Reds remain fifth but their hopes of qualifying for next season’s Champions League have been hurt by a defeat that means sixth-placed Chelsea will go above them if they beat Aston Villa on Wednesday.
Liverpool’s first defeat in five games in all competitions will raise fresh questions about Slot’s Anfield future.
This was the first of Liverpool’s two trips to Molineux in the space of four days, with an immediate chance for revenge in the FA Cup fifth round on Friday.
Slot this week said he no longer finds Premier League matches a “joy to watch” due to the rise in set-piece goals, and Liverpool supporters took no pleasure from this dismal performance.
Wolves and Liverpool fans joined in a sustained round of applause on 18 minutes in memory of Diogo Jota, who wore that shirt number during his time at Molineux before joining the Reds.
Portugal forward Jota died in a car crash in Spain last year. (AFP)
Edited by Cecil Wong
