The two clashes between the Premier League heavyweights, who have 20 League Cup wins between them, were the standout ties from the fourth round draw.
It will be the 15th time that Liverpool have played Arsenal in the competition, the most played fixture in the history of the tournament.
Manchester United meanwhile will play Chelsea for the fifth time and the first since a thrilling fourth round encounter in 2012, that saw the Londoners win 5-4.
They also met at Stamford Bridge in the fifth round of the FA Cup back in February, where first half goals from Paul Pogba and Ander Hererra secured victory for Ole Gunnar Solskjaer's side, who needed a penalty shootout to squeeze past League One Rochdale in round three.
Elsewhere, holders Manchester City were drawn at home to Southampton as they bid to win the competition for a fifth time in seven seasons. Aston Villa host Midlands rivals Wolves while Everton will take on Watford at Goodison Park.
Leicester are the only Premier League side to face lower league opposition in the form of a trip to last season's semi-finalists Burton, who beat Premier League Bournemouth 2-0 to reach this stage.
Oxford United caused one of the shocks of the third round when they thrashed West Ham 4-0. They were rewarded with a draw to face League One rivals Sunderland, who won 1-0 at Sheffield United.
There is also an all-League Two clash as Colchester, who beat Tottenham on penalties, take on Crawley, who also needed spot-kicks to knock out Championship side Stoke.
That draw means there is guaranteed to be a League Two side in the quarter-final for only the third time since the EFL was re-branded in 2004.
For the first time in the competition's 59-year history, no Championship side made it through to the fourth round.
Ties will be played on the week commencing 28 October 2019.
Carabao Cup fourth Draw:
- Everton v Watford
- Aston Villa v Wolves
- Manchester City v Southampton
- Burton Albion v Leicester
- Crawley v Colchester
- Chelsea v Manchester United
- Oxford v Sunderland
- Liverpool v Arsenal