Brendan Rodgers' side came into the game looking to banish the memories of last term's corresponding fixture, Steven Gerrard's slip and the defeat which halted their trophy charge.
But they again shot themselves in the foot, with slack defending allowing Gary Cahill and Diego Costa to overturn Emre Can's first Liverpool goal and move Chelsea a daunting 15 points clear of the Merseysiders.
Much had been made of Rodgers' team selection away to Real Madrid in midweek, with the likes of Gerrard, Mario Balotelli and Jordan Henderson recalled after being omitted from the starting line-up for the UEFA Champions League clash.
Yet it was one of the supposed second string to have impressed in the Spanish capital, Can, who put the hosts ahead early on with an effort that deflected in off Cahill.
The England man - perhaps fortunate to twice go unpunished for handball in the Chelsea area - atoned just five minutes later, though, bundling home despite Simon Mignolet's best efforts.
Jose Mourinho's approach was much more attacking than the April smash-and-grab - a reward coming after 67 minutes as a string of Liverpool lapses at the back were punished by Costa's clinical finish.
Still undefeated, Chelsea have now taken five points from a possible nine away to Manchester City, Manchester United and Liverpool to firmly underline their credentials as England's best this campaign.
Can was one of just three outfield players retained from the Madrid fixture and gave Liverpool a ninth-minute lead thanks to a sizeable nick off Cahill.
But Cahill quickly had Chelsea level, reacting quickest to prod towards goal after Mignolet had sharply denied John Terry from a corner, with technology confirming the Belgian had carried the ball over the line.
An already high-charged atmosphere was ramped up as claims for a Cahill handball in the penalty area fell on deaf ears before Costa introduced himself to the contest by shoving Martin Skrtel towards an onrushing Mignolet, earning a warning from referee Anthony Taylor.
A semblance of composure returned to the game but Chelsea looked increasingly dangerous on the break - especially behind the adventurous Alberto Moreno at left-back for Liverpool - as they built pressure prior to the interval.
The second period began at much more sedate tempo, Costa's wayward overhead effort and Thibaut Courtois' save from Raheem Sterling representing rare flashpoints.
Yet the hosts were perhaps the architects of their own downfall as Chelsea moved ahead.
Substitute Willian found Cesar Azpilicueta on the left flank, with Glen Johnson out of position, and Philippe Coutinho did little to halt the Spaniard's progress to the byline.
Azpilicueta's cut-back was palmed into a dangerous area by Mignolet, allowing Costa to power home for his 10th league goal of the season.
With Fabio Borini and Rickie Lambert thrown on as Liverpool sought a dramatic equaliser, a blatant Cahill handball went unnoticed in the dying embers, leaving Mourinho to calmly acknowledge victory in stark contrast to his tub-thumping celebrations from last term.
