Manchester United will host rivals Manchester City at Old Trafford, in what will be the first clash between Jose Mourinho and Pep Guardiola in the competition.
Another derby drawn out was West Ham United against Chelsea at the London Stadium, while eight-time winners Liverpool were paired with Tottenham Hotspur.
Arsenal welcome Reading to the Emirates Stadium, and there's an all-Premier League match-up between Southampton and Sunderland at St Mary's.
Read more: EFL Cup Round Three review
Elsewhere, Sky Bet Championship high-fliers Norwich City and Newcastle United were drawn against Leeds United and Preston North End respectively, and two of Round Three's late winners, Bristol City and Hull City, will meet at Ashton Gate.
EFL Cup Round Four draw in full:
West Ham United v Chelsea
Manchester United v Manchester City
Arsenal v Reading
Liverpool v Tottenham Hotspur
Bristol City v Hull City
Leeds United v Norwich City
Newcastle United v Preston North End
Southampton v Sunderland
Ties due to be played week commencing 24th October 2016.