Shortly after beating Bournemouth 3-1 in the League Cup Quarter Final, the reds were handed a difficult semi final tie against Premier League pacesetters Chelsea.
The reds will meet Mourinho's men over two legs in the last two weeks of January - the first leg at Anfield.
In the other game, Tottenham Hotspur and Sheffield United will battle it out for a trip to Wembley.
LFC boss Brendan Rodgers, formerly a member of Mourinho's coaching staff, has yet to beat Chelsea since joining Liverpool. He drew twice in his first season at Anfield, before losing twice last season and once more earlier this season.
Ties will be played week commencing 19th and 26th January 2015.