On the same night, Manchester City go to Club Bruges, while on Wednesday, neighbours United host Atalanta, and Chelsea face Malmo at Stamford Bridge.
Here, we look at the four English teams’ European opponents this week.
Luis Suarez will be gunning for his old club when Liverpool head to Madrid.
The 34-year-old scored 82 goals in 133 games for the Reds, and will doubtless be keen to put one over his former employers.
Uruguay hitman Suarez last faced Liverpool when his Barcelona side was hammered 4-0 at Anfield in 2019.
Atletico also dumped then-reigning champions Liverpool out of the tournament at the last-16 stage in March 2020.
They have lost just once in La Liga so far this term and currently sit second in Group B behind Liverpool.
Belgium’s surprise Champions League package will be bidding for another upset when hosting Manchester City on Tuesday.
The Belgium champions pulled off a stunning 1-1 draw with Paris St Germain, thwarting Lionel Messi, Neymar and Kylian Mbappe into the bargain.
Then Bruges beat RB Leipzig 2-1 to put themselves ahead of City in the Group A standings. Pep Guardiola’s men will expect to reverse that this week, but the resolute hosts will be itching to deliver on the shock factor once more.
Gian Piero Gasperini’s buoyant Atalanta will head to Old Trafford on Wednesday to face Manchester United in a bid to remain top of Group F.
Josip Ilicic broke his season-long domestic duck with two goals on Sunday as Atalanta thrashed Empoli 4-1 in Serie A.
The Italians will hope to pile more misery on an off-colour United, after winning 1-0 at Young Boys and clawing a 2-2 draw with Villarreal.
Jon Dahl Tomasson’s Swedish outfit cannot arrive at Stamford Bridge to face Chelsea in Wednesday’s Group H clash with much in the way of expectation.
Malmo have shipped seven goals in two defeats, going down 4-0 at Zenit and 3-0 at home to Juventus.