The Reds will be looking to go one better in this season’s tournament, after falling to defeat to Manchester City in last term’s final in February.
Due to ongoing redevelopment work at Anfield, the Reds were given special dispensation to ensure their second-round clash was an away tie.
Burton currently ply their trade in the Championship, and are managed by ex-Liverpool striker Nigel Clough, son of legendary Nottingham Forest manager Brian Clough.
This will be the first time the two sides have met in history.
The Brewers sealed promotion to the English second tier by virtue of a second-placed finish in last season’s League One competition.
The Reds are the record League Cup winners, having secured the trophy on eight occasions, and will be looking to make it nine as they enter the 2016/17 tournament.
Clough spent three years with Liverpool between 1993 and 1996, having joined from Forest in a deal worth £2.75 million, but made just 44 appearances, scoring nine goals.