Goals from Nicolas Anelka and a stoppage-time strike by Florent Malouda took the Londoners two points clear of Manchester United.
Chelsea have faced Liverpool on numerous occasions in recent seasons and the first half was a reflection on just how well the players know each other.
They cancelled each other out so well it took 25 minutes for Jose Reina to be called into action when he clutched the ball out of the air from a Didier Drogba header following Anelka's byline cross.
Three minutes later Reina repeated the effort, this time diving low to keep out Anelka's glancing header.
Liverpool's first effort came from the right foot of Steven Gerrard on 30 minutes. But his 25-yard right-footed free-kick sailed high over Henrique Hilario's crossbar.
Michael Ballack had a free header from Deco's right-wing free-kick on 35 minutes but it also failed to trouble Reina's goal.
Michael Essien decided to get into the shooting action on 38 minutes, but Reina snuffed out the left footer expertly.
On the stroke of half-time Hilario pulled off the save of the game by turning away a 35-yard, left-footed curling free-kick by Albert Riera.
Gerrard had a snap header from 18 yards out three minutes after the restart but his effort was well wide.
He followed that up with a strong 25-yard effort that inched over Hilario's crossbar.
The Blues finally broke the deadlock on 60 minutes when Frank Lampard took the ball off Javier Mascherano in midfield.
Essien picked it up and passed to Deco who fed Drogba on the left. The Ivory Coast hitman, on the left, sent the perfect left footer across the six-yard box and up popped Anelka to tuck the ball home past a hapless Reina.
Liverpool reacted with excellent possession and attacked the Chelsea defence without ever getting through.
And with seconds remaining Chelsea nabbed their second. Drogba, on the right, cut the ball back to the onrushing Malouda who tucked the ball home past Reina.
In the last few seconds, Yossi Benayoun somehow screwed the ball wide with Hilario on the floor and the Chelsea goalkeeper then produced another fine save to thwart Gerrard in the dying seconds.
Liverpool perhaps deserved a point but they lacked what Chelsea had - the killer instinct in front of goal.