Michael Beale's side will start with an away trip to Ipswich Town on Sunday October 2 at Portman Road, with a 1pm BST kick-off.
The competition, which has replaced the U21 Premier League Cup, follows a Champions League-style format, as 32 teams compete in the main group phase with the top two from each pool advancing to the last 16.
The last 16, quarter-finals, semi-finals and final will all be one-off, knockout ties, with extra-time and penalties required if the teams are level after 90 minutes.
Watch the U23s hit Spurs for six on LFCTV GO
Liverpool's Premier League U23 Cup fixtures:
Sunday October 2: Ipswich Town (A) 1pm, Portman Road.