John Arne Riise put Liverpool ahead in the first-half before Spaniard Luis Garcia extended the lead early in the second period.
Ivory Coast striker Didier Drogba pulled on back for Chelsea, who were looking to win the domestic double, in the 70th minute but it was not enough to hand the Blues a place in the final.
Liverpool will play the winners of Middlesbrough and West Ham, who clash on Sunday.
Chelsea's Portuguese coach Jose Mourinho opted for a defensive-minded midfield, leaving dangerous trio Joe Cole, Arjen Robben and Damien Duff on the bench.
Liverpool had the upper hand in the first-half as Steven Gerrard and Harry Kewell moved well on the flanks, swinging several dangerous crosses.
Drogba should have put Chelsea in front against the run of play in the 19th minute, as a clear offside was not awarded to Liverpool, but the Ivorian international's shot went wide.
Riise broke the deadlock just one minute later through an awarded indirect free kick. The Norwegian exchanged the ball with Gerrard before curling the ball through Chelsea's wall into the back of the net.
Five minutes after the re-start, Chelsea defender John Terry headed Arjen Robben's free kick into the net but the goal was denied by the referee who awarded a foul to Liverpool left back Riise.
In the 53rd minute, Garcia pounced on a poor header from William Gallas before sending a superb volley into the top corner of the net.
Drogba narrowed the gap in the 70th minute when he capitalized on a poor clearance header by Riise before heading the ball past Reina.
Unmarked Joe Cole missed a rare chance to equalize in the stoppage time when he controlled the ball on his chest inside the area but his close-range effort went poorly wide.