The Reds progressed by securing a 6-1 aggregate victory over FC Porto with a 4-1 win in Wednesday's last-eight second leg at Estadio do Dragao.
Barcelona, who reached the semi-finals by defeating Manchester United, will host the first leg of the tie on Tuesday April 30/Wednesday May 1, with the second leg to take place at Anfield on Tuesday May 7/Wednesday May 8.
Full fixture and ticket details will be announced on Liverpoolfc.com in due course.
Tottenham Hotspur and AFC Ajax will contest the other semi-final.