Having not played at the national stadium for 16 years they followed up last month's Carling Cup triumph by securing a place in the last four with a hard-fought victory.
Luis Suarez put the hosts ahead midway through the first half and although former Reds striker Peter Crouch equalised quickly, Stewart Downing's second goal of the season knocked out last year's runners-up.
Earlier in the day, Fernando Torres finally ended his goalscoring drought as his brace helped Chelsea book another visit to Wembley with a comfortable 5-2 victory over Leicester at Stamford Bridge.
Early goals from Gary Cahill and Salomon Kalou set the Blues on their way as Roberto Di Matteo maintained his 100 per cent winning start to his tenure as Chelsea boss.
Torres added the third after 67 minutes to end a spell of 25 hours 41 minutes of football for Chelsea without scoring and grabbed his second with a late header before turning provider to set up a last-minute Raul Meireles goal.
Jermaine Beckford and Ben Marshall scored consolation goals for the visitors, who lacked the quality in possession to ever truly test the Blues.
Chelsea will now face either Tottenham or Bolton in the semi-finals, while Liverpool will meet Everton or Sunderland.