Arsene Wenger’s side beat Coventry City in the fourth round of the competition, winning 4-0 at the Emirates on Friday night.
Liverpool booked their place in the fifth round draw with their 2-0 victory at Bournemouth on Saturday afternoon.
The last time the sides met in the FA Cup was back in a third round clash at Anfield in 2007. The Gunners ran out 3-1 winners thanks to a brace from Tomáš Rosický, and one from Thierry Henry. Dirk Kuyt got Liverpool’s only goal that day.
The draw was made by father and son Troy and Andros Townsend at Wembley Stadium on Sunday afternoon.
The game will be played over the weekend of 15/16 February 2014 – a week after the two sides face each other at Anfield in the Premier League.
Wenger’s side face Man United and Bayern Munich either side of the match, while Liverpool are in London at Fulham for the midweek fixture prior to the tie.
The full draw is as follows:
Manchester City vs Chelsea
Sheffield United/Fulham vs Nottingham Forest/Preston
Arsenal vs Liverpool
Sheffield Wednesday vs Charlton Athletic
Brighton v Hull
Everton vs Swansea City
Cardiff City v Wigan
Sunderland vs Southampton