Collingwood and Kevin Pietersen shared in England's highest fourth-wicket partnership in Ashes Tests as they pushed the tourists towards an unbeatable target on a benign pitch.
Collingwood was out in the final over before tea for 206, caught behind attempting to drive Stuart Clark, with Pietersen not out 146 and England going to the interval at 468 for four.
Collingwood's patient double century in 516 minutes off 392 balls was the first by an England batsman in Australia since Wally Hammond's 231 in Sydney in 1936.
The records kept tumbling with Collingwood-Pietersen's 310-run stand in 354 minutes, bettering the 288 shared by Nasser Hussain and Graham Thorpe at Edgbaston in 1997 as the highest England fourth-wicket partnership in Ashes cricket.
The pair have put England in a position to level the series after losing by 277 runs in Brisbane, if they can bowl out the Australians twice on an unresponsive Adelaide pitch.
It was Collingwood's third Test century and first against Australia and followed the heartbreak of getting dismissed for 96 in the second innings of the first Brisbane Test.
He scored 134 not out against India in the first Test at Nagpur last March and 186 against Pakistan at Lord's in July.
Pietersen claimed the second century in his last three Ashes Tests off a belligerent 149 balls, clubbing Glenn McGrath for three fours in one over and raising his hundred with a scampering single off Stuart Clark before lunch.
By tea, Pietersen had batted for 354 minutes and hit 14 fours and a six in his 239-ball stay.
He ran down the field holding his bat and helmet aloft in jubilation before a warm embrace from Collingwood on attaining his sixth century in his 20th Test.
It was Pietersen's 158 off 187 balls in the drawn 2005 fifth Test at The Oval that helped England clinch the Ashes, which stands as his highest score in Tests.
Test cricket's greatest wicket-taker Warne even resorted to bowling outside leg-stump in an attempt to get Pietersen to commit to a rash shot. He went to tea with a century of his own at 0-129 off 42 overs.
It was Warne's worst Test return in an Ashes Test against England and ranked second only to his worst of 0-147 against India in Calcutta in 1998.
At tea, Lee had the figures of 1-126 off 30 overs, Glenn McGrath 0-86 off 28 overs and Stuart Clark 3-67 off 28.5 overs.
Australia thought they had Pietersen out on his overnight score of 60 early in the morning with a confident appeal for caught behind off Lee.
Lee ran triumphantly down the pitch acclaiming the catch, but West Indian umpire Steve Bucknor remained unmoved and television replays suggested Pietersen's bat narrowly missed the ball.