The meeting at Anfield gives both clubs another demanding cup test after they came through difficult third-round ties.
Chelsea produced a nine-goal thriller against Leeds, winning 6-3, while Liverpool secured a 3-1 victory over Tottenham. Arsenal also progressed with a 4-2 win away to Ipswich.
Brighton provided one of the biggest surprises of the round by knocking Manchester United out at Old Trafford with a 3-2 victory.
Peterborough were the only team to progress via penalties, beating Barnsley 7-6 in the shootout after the sides had drawn 3-3.
There are also two other all-Premier League meetings, with Everton hosting Newcastle and Sunderland facing Brentford.
Bradford City and Peterborough have been drawn together, while Fulham will meet Crystal Palace and Bournemouth take on Aston Villa.
The final place in the fourth round will be decided when holders Manchester City host Norwich on Thursday night.
The fourth-round ties are scheduled to take place during the week commencing October 26.
Carabao Cup fourth-round draw
Fleetwood vs Arsenal
Manchester City or Norwich vs Brighton
Everton vs Newcastle
Sunderland vs Brentford
Liverpool vs Chelsea
Bradford City vs Peterborough
Fulham vs Crystal Palace
Bournemouth vs Aston Villa
Chelsea manager Xabi Alonso has given his players every chance of returning for Friday's Premier League meeting with Brentford, with Joao Pedro, Reece James and Moises Caicedo all still in contention.
Romeo Lavia believes he is finally benefiting from the work he has put into overcoming his injury problems as he looks to establish himself at Chelsea.
Elliot Anderson has revealed how facing Manchester City as a youngster left him dreaming of one day playing for the club.
Tottenham Hotspur have received a welcome injury boost with Pedro Porro set to return for Saturday's Premier League meeting with Aston Villa.
