Glen Johnson's late winner gave Liverpool victory as Chelsea's indifferent run of form continued.
The Reds recorded a Premier League double over Chelsea last season - and secured three points again as Johnson produced a moment of individual brilliance to clinch victory with three minutes left.
The recalled Maxi Rodriguez crowned a sweeping passing move to give the visitors a half-time lead, but Blues boss Andre Villas-Boas looked to have changed the course of the game when substitute Daniel Sturridge equalised after the interval.
Johnson made his spectacular intervention against his former club just as the points looked set to be shared, taking Charlie Adam's pass in his stride before cutting through the hosts' defence to beat Petr Cech.
Liverpool manager Kenny Dalglish celebrated wildly on the touchline, but it was total despair for Villas-Boas as Chelsea slumped to their third loss in four Premier League games.
And of great concern to Villas-Boas will be the fact that their high-profile meetings with Manchester United, Arsenal and now Liverpool have all ended in defeat.
The Londoners stand 12 points behind leaders Manchester City and on this evidence their hopes of winning the title may have already disappeared.
Chelsea officials insisted before kick-off that reports of the first cracks surfacing in the relationship between Villas-Boas and owner Roman Abramovich were "total nonsense", but there is no question their form has deteriorated after a competent rather than spectacular start to the season.
For Liverpool, the joy at the final whistle was a world away from the jeers that greeted the goalless draw with Swansea at Anfield in their last league game.
Villas-Boas and Dalglish left £85m of striking talent on the bench as £50m Fernando Torres missed out on the chance to start against his former club and Andy Carroll was excluded from Liverpool's starting line-up.
They only made late appearances, with Torres introduced in a vain attempt to win the game for Chelsea and Carroll emerging as Liverpool tried to ensure they would hang on to their lead.
Chelsea's first-half display was lamentable but they did create an early opportunity when Juan Mata fired across the face of goal, while large sections of the Stamford Bridge crowd thought they had taken the lead when Didier Drogba's free-kick hit the side-netting.
Liverpool, in contrast, were composed and ordered with the movement of Luis Suarez and Craig Bellamy a constant threat, especially to the indisciplined David Luiz.
Chelsea were unable to pierce the visitors' midfield and the visitors went ahead after 33 minutes when Jon Obi Mikel conceded possession to Adam in dangerous territory. Suarez then found Bellamy, whose perfect pass was an open invitation for Maxi to sweep his finish past Cech.
Dalglish's side ended the opening 45 minutes in complete command - forcing Villas-Boas to respond by removing the labouring Mikel and sending on Sturridge.
The change was rewarded 10 minutes after the restart when Florent Malouda was allowed too much time and space to run into the area before crossing for Sturridge to tap in to an unguarded net.
As the momentum changed, Pepe Reina produced a brilliant save from Branislav Ivanovic's low header with Chelsea sensing the game was now turning in their favour.
Liverpool, for the first time, were in retreat and Malouda should have put Chelsea in front with 16 minutes left, only to scuff a finish across the face of goal with Reina exposed.
Chelsea introduced their two former Reds players, Torres and Raul Meireles, with six minutes left - but it was Dalglish's side that immediately had a chance to regain their advantage.
Substitute Jordan Henderson skipped past a succession of challenges to allow Downing to set up Dirk Kuyt who shot wastefully wide, much to Dalglish's obvious disgust.
Chelsea failed to heed the warning and Liverpool made no mistake when they created another opportunity with three minutes remaining.
Adam's raking pass found Johnson, who evaded Ashley Cole and Malouda to score with great composure and give Liverpool their latest Stamford Bridge win.