Bruno Cheyrou's first league goal for Liverpool got the Reds' Champions League push back on track and dented Chelsea's title challenge.
Cheyrou's first-half goal followed a fine piece of build-up play by Emile Heskey and deflated Chelsea.
Liverpool were made to sweat late on when El-Hadji Diouf was sent off following a tangle with Adrian Mutu.
Reds keeper Jerzy Dudek also limped off late on to hand a debut to Patrice Luzi but by then Chelsea were beaten.
Chelsea must have known it was not going to be their night as early as the 11th minute as striker Hernan Crespo limped off with a pulled calf muscle, Eidur Gudjohnsen an early deputy.
Yet, surprisingly, it was the Liverpool attack which carried the most threat, despite Michael Owen's return from injury being limited to a place on the substitutes' bench.
In Owen's continued absence, Heskey played the lead striker's role following his late salvage job in the FA Cup at Yeovil on Sunday.
11 mins: Crespo limps off with calf injury
32 mins: Cheyrou sweeps home Heskey cross
80 mins: Liverpool keeper Dudek limps off
89 mins: Diouf sent off following tangle with Mutu
England striker Heskey served early notice of his intent on 13 minutes with an almost undefendable low centre across the face of goal that Cheyrou just failed to turn home.
But that combination clicked brilliantly on 32 minutes, with Heskey again the architect and Cheyrou the scorer with his first league goal for Liverpool.
Heskey did well to chest down a high ball on the half-way line and played a one-two with Cheyrou before racing out wide.
And when his second inviting low cross of the night came in John Terry was this time unable to clear, allowing Cheyrou to sweep home past helpless goalkeeper Carlo Cudicini.
Chelsea's response was a Joe Cole shot which flew just wide and a stinging Lampard drive over the crossbar from an Adrian Mutu lay-off.
Gudjohnsen had earlier gone close following the home side's best move of the night, volleying wide after Cole had flicked on Makalele's pass.
But the home side were unconvincing and the home fans frustrated.
Those frustrations turned to anger midway through the second half as Chelsea's continued impotency prompted Claudio Ranieri to withdraw Cole at the expense of winger Jesper Gronkjaer.
The impish Cole was not a popular sacrifice and Gronkjaer struggled to make a further impact as Liverpool dug in their heels.
But Liverpool's cause was not helped by a late red card for Diouf for a petulant second yellow card and a thigh injury to goalkeeper Dudek, prompting a debut for Corsican-born goalkeeper Luzi.
Luzi's first job was almost to pick the ball out of the net as Mutu flicked a header against the crossbar from a corner.
But in fact his first touch in the Premiership was a fine save at the feet of Mutu as the Romanian striker looked destined to end his goal drought.
Mutu also had a frantic penalty claim waved away after Sami Hyypia tumbled over his shoulder late on but Cheyrou remained the unlikely hero.
His goal secured a valuable victory for Houllier's side, revenge for an opening-day defeat at Anfield and means Chelsea's search for a league double over Liverpool now stretches 84 years.
Chelsea: Cudicini, Johnson, Gallas, Terry, Bridge, Makelele,
Lampard, Cole (Gronkjaer 62), Geremi, Crespo (Gudjohnsen 12),
Subs not used: Sullivan, Babayaro, Desailly.
Liverpool: Dudek (Luzi Bernardi 77), Henchoz, Hyypia, Traore,
Biscan, Diouf, Murphy, Hamann, Cheyrou (Riise 77), Heskey,
Subs not used: Smicer, Owen, Le Tallec.
Sent off: Diouf (87).
Booked: Heskey, Diouf.
Sent off: Diouf.
Referee: S Dunn (Gloucestershire).