The draw was made live from Anfield on Monday evening and saw Julen Lopetegui’s side pitted against fellow Premier League opposition.
The Reds won the trophy last season and will begin their defence against Wolves in Lopetegui’s fifth match in charge of the club.
Last year, the old gold beat Sheffield United in the third round at Molineux, before bowing out to Norwich City at the fourth round stage.
Date and ticket information for the Anfield tie will be announced in due course.