Liverpool have won two and Chelsea one of the clubs' recent battles in Europe, but the Blues won the most recent in last year's semi-finals.
Rafa Benitez's side won the 2004/05 semi-final, before the teams locked horns in the 2005/06 group stage. Liverpool then won the 2006/07 semi-final against Chelsea, who turned the tables under Avram Grant in last season's semis.
Holders Manchester United play Portuguese champions FC Porto, while Arsenal meet Villarreal of Spain.
Arsene Wenger's team beat the Spaniards in the 2006 last four before losing to Barca in the final.