England were indebted to opener Andrew Strauss’s nearly six hour-long 129. But the left-hander gave Warne his 31st five-wicket haul in a Test innings when he was smartly caught off bat and pad by Simon Katich at silly mid-off.
Strauss faced 210 balls with 17 fours.
"I think we’re just slightly ahead," Warne told reporters after stumps.
England, as they had done for much of the series, were going well against Australia’s quicks before Warne came on in the 14th over and were 82 for nought when the legendary leg-spinner, the only man to take 600 Test wickets, began a spell of four for 16 in 38 balls.
Strauss and Andrew Flintoff (72) then revived the innings with a fifth-wicket stand of 143 in nearly 37 overs before Warne caught the all-rounder at slip off Glenn McGrath.
"At one stage when Freddie and Straussy were batting pretty well we were starting to stare down the barrel a little bit but we fought back. It’s been a trademark of the series," added Warne. "But it’s probably the best we’ve bowled on day one in the last couple of games.
The Hampshire captain, who also said he felt tired and admitted to a slightly sore shoulder after bowling almost double the number of overs of any other bowler, praised Strauss’s innings despite having labelled the batsman the "new Daryll", a reference to South Africa batsman Daryll Cullinan whom he dismissed on several occasions.
"He played well, he hung in there and toughed it out. For me, it’s hard when you bowl day one because there’s not a lot on offer.
"You need subtle variations and change of pace," said Warne, whose current series haul of 33 wickets is the most by any Australian bowler in a five-match series in England.
Strauss said of his century: "In terms of importance it’s probably the best I’ve ever played. Today was a massive day in the context of the series and it was vitally important that at least one of us went on and got a hundred.
"It’s fairly positive," added Strauss of England’s mood. "Being 131 for four, we’ve come back pretty well."
England would have been aiming for a score of around 500 after captain Michael Vaughan won his third straight toss of the series.
There was certainly no guarantee that a first innings score of above 400 would be insurance against defeat, as South Africa showed when they made 484 against England at The Oval two years ago only to lose by nine wickets.
However, Australia’s star-studded top order have proved vulnerable so far this series, with their best first innings score 308.
England had recovered from Warne’s initial burst to be 213 for four at tea.
Strauss was 92 not out and Flintoff, playing an intelligent innings, unbeaten on 39.
Flintoff completed a 79-ball fifty with his ninth four, a sweep off Warne
Strauss, in his first Ashes campaign, scored his second century of the series and seventh in Tests when he drove fast bowler Brett Lee through mid-on for his 13th four.
Flintoff then lofted Warne straight for the first six of the day but fell tamely, his 115-ball innings with one six and 12 fours helping England to 274 for five.
His exit brought in Paul Collingwood, scorer of six championship hundreds this season, and chosen ahead of fast bowler James Anderson to fill the gap created by paceman Simon Jones’s ankle injury.
But the Durham all-rounder managed just seven before he was lbw to first change Shaun Tait.
England resumed after lunch on 115 for three, Strauss 42 not out and Kevin Pietersen 10 not out.
Pietersen fell soon afterwards when he was bowled by county skipper Warne hitting across the line.
Ever the showman Warne, 36 next week responded to a slow handclap from some sections of the 23,000 capacity crowd, unhappy at the time he was taking to bowl his overs, by cupping his hand to his ear.
Earlier Warne had Strauss’s fellow left-handed opener Marcus Trescothick, still searching for his first Test hundred against Australia, brilliantly caught by Matthew Hayden, going low to his left at first slip, for 43.
He then saw Vaughan chip to Michael Clarke at mid-wicket before Ian Bell was lbw for nought.
England’s two victories in the series to date, in the second and fourth Tests, at Edgbaston and Trent Bridge respectively, had with imposing totals batting first against an attack minus McGrath.
However, the veteran quick was passed fit following a right elbow injury and returned in place of Michael Kasprowicz.