A late brilliant individual effort from former Blues defender Glen Johnson did the damage for the Reds who struck first through Maxi Rodriguez before substitute Daniel Sturridge answered for the home side.
Chelsea sent on ex-Reds pair Fernando Torres and Raul Meireles in the second half in a bid to unsettle their former teammates but the visiting side had the laugh last with Johnson providing the winning goal which inflicted a second loss in a row at Stamford Bridge since 2002 following the Blues' 5-3 defeat to Arsenal last time out.
Liverpool scored the opener in the 34th minute after a fantastic build-up. Charlie Adam dispossessed John Obi Mikel just outside the area with Craig Bellamy picking up the scraps before playing a one-two with Luis Suarez and finding an unmarked Maxi Rodriguez who slotted home neatly past Petr Cech for his first goal of the season.
Andre Villas-Boas made a vital change at half-time with Daniel Sturridge, who replaced John Obi Mikel, netting the leveler ten minutes into the second half with a simple tap-in from close range from Florent Malouda's mishit shot on goal from the left side of the area.
Chelsea had a number of chances early in the second half and they were made to pay for their profligacy as Liverpool produced a winner in the 88th minute through former Blues man Glen Johnson. He took a neat first touch from Charlie Adam's pass before rounding Ashley Cole and advancing into the area to slot home with his left foot.
Earlier in the piece, Didier Drogba's free-kick in the 21st minute evaded the Liverpool wall and kept Reina rooted to the spot but fortunately for the visitors it was inches wide of the mark as the Spaniard asked the question of his defence.
Just before half-time, Suarez got free from his marker David Luiz only to see the Brazilian make good ground to block his attempt into the side netting.
Early in the second half, Drogba skipped through the Reds defence but could only put his shot over the bar before his free-kick was met by Branislav Ivanovic's glancing header but Reina came up with a remarkable goal-line save to deny the Blues defender.
Chelsea began to really press the Liverpool side after their equaliser and again came close in the 70th minute when Malouda controlled with his chest before trying his luck with an overhead attempt five minutes before missing the target from the back post with Frank Lampard and Juan Mata waiting for a tap-in.
It looked as though the home side would go on to take maximum points bar for a late flurry of attack from Kenny Dalglish's side and it paid dividends with Johnson's winner sending the Anfield club back to sixth and extending their unbeaten run to seven matches as the Blues remained fourth despite a third defeat in their past four league outings.