Their reward for beating Leicester is a trip to West Ham United’s new ground in the week commencing 24 October.
The Hammers, the first team out of the hat, needed a 96th-minute Dimitri Payet free-kick to see off League Two Accrington Stanley.
Chelsea last met West Ham in this competition in 2004/05, Mateja Kezman scoring the only goal at Stamford Bridge. That was in the third round and Chelsea went on to lift the trophy that season.
Ticket details will follow in due course.
The full draw is:
West Ham United v Chelsea
Manchester United v Manchester City
Arsenal v Reading
Liverpool v Tottenham
Bristol City v Hull
Leeds United v Norwich City
Newcastle v Preston North End
Southampton v Sunderland