The Reds have been pitted against Stoke City, Southampton and Reading and will face each team once, either home or away. Dates and venues of the fixtures are still to be confirmed.
The six group winners and two best runners-up will progress to the quarter-final of the competition.
Last season, Liverpool reached the last-eight stage, where they were defeated by Tottenham Hotspur.
The Reds will face the same opponents in the U16 version of the tournament.
U18 and U16 Premier League Cup draw
Group A: Wolverhampton Wanderers, Middlesbrough, Swansea City, Tottenham Hotspur
Group B: Liverpool, Stoke City, Southampton, Reading
Group C: Sunderland, Derby County, Brighton & Hove Albion, Aston Villa
Group D: West Bromwich Albion, Everton, Arsenal, Fulham
Group E: Manchester City, Blackburn Rovers, Leicester City, West Ham United
Group F: Manchester United, Newcastle United, Chelsea, Norwich City