Liverpool lifted the Community Shield, thanks to Peter Crouch's 80th-minute winner at the Millennium Stadium.
Crouch celebrates his winner
A tepid second half looked to be drifting towards penalties when Crouch rose to head in Craig Bellamy's cross.
Liverpool, with Steven Gerrard on the bench, went ahead when John Arne Riise ran 60 yards before beating Carlo Cudicini with a dipping shot.
But £30.8m striker Andriy Shevchenko equalised before the break, guiding home Frank Lampard's inviting pass.
Victory will be particularly sweet for Rafael Benitez, who began the match with skipper Gerrard, £6m signing Bellamy and Xabi Alonso on the bench.
By contrast, Chelsea counterpart Jose Mourinho packed summer arrivals Shevchenko and Michael Ballack into his side alongside established first-teamers Frank Lampard, Didier Drogba and Arjen Robben.
But while Liverpool may have lacked the star power of their opponents, they were the more cohesive unit in the first half.
Shevchenko scored his first goal in English football
Chelsea fans had only just been revelling in the way Shevchenko had pressurised the Liverpool defence into conceding a corner when they saw their team go behind.
Steve Finnan headed clear and Riise ran almost the length of the pitch unchallenged before unleashing a 25-yard shot which Cudicini perhaps should have saved.
Mourinho looked on in disgust, arms folded.
His mood worsened when first Lampard was booked for a petulant kick on Bolo Zenden and then Ballack, yellow-carded after seven minutes, hobbled off with an apparent hip injury midway through the first half.
Liverpool could have made it 2-0 when the lively Mark Gonzalez slid a dangerous pass across goal and the ball came off Luis Garcia but Cudicini redeemed himself by tipping over under pressure from Crouch.
But while his team-mates struggled, Shevchenko shone and the Ukrainian drew Chelsea level on 43 minutes.
Lampard provided the pass, which Shevchenko controlled beautifully before coolly slotting past Reina.
The Shevchenko show continued in the second half, the former AC Milan star forcing Reina to tip a header round the post.
But as Chelsea began to take charge of proceedings, Benitez first brought on Gerrard and Alonso, then moments later introduced Bellamy.
It was the Wales striker, making his club debut at Cardiff's Millennium Stadium, who made the difference in the end.
His electric pace saw him break clear down the left and he delivered a fabulous cross for Crouch to head in from close range.
Brazilian substitute Fabio Aurelio might even have made the scoreline more emphatic but he was denied by a sharp Cudicini save.
Chelsea: Cudicini, Paulo Ferreira (Mikel 81), Terry, Ricardo Carvalho, Essien, Geremi (Bridge 53), Ballack (Kalou 26), Lampard, Shevchenko, Drogba (Wright-Phillips 71), Robben (Diarra 62).
Subs Not Used: Hilario, Mancienne.
Booked: Ballack, Lampard, Diarra.
Goals: Shevchenko 43.
Liverpool: Reina, Finnan, Agger, Carragher, Riise, Pennant (Gerrard 60), Sissoko, Zenden (Alonso 60), Gonzalez (Aurelio 56), Crouch (Sinama Pongolle 89), Luis Garcia (Bellamy 66).
Subs Not Used: Dudek, Hyypia.
Goals: Riise 9, Crouch 80.
Ref: M Atkinson (W Yorkshire).