The master leg-spinner, who was given a standing ovation by the near-capacity crowd as he came into the attack in the 41st over, bowled opener Andrew Strauss for 50 to become the first bowler in Test history to take 700 wickets.
Warne, who has announced he is retiring from Test cricket after the last two Tests of this series, produced a signature leg-break to knock over Strauss' middle-stump and ignite wild celebrations in the crowd here on Tuesday.
Warne, 37, is playing in his 144th Test and has been acclaimed as one of the all-time cricketing greats, having revolutionised the art of wrist-spin bowling.
Warne's dismissal of Strauss left England struggling at 117 for four off 52 overs at tea after winning the toss with Kevin Pietersen not out three and captain Andrew Flintoff on 13. Warne had 1-21 off six overs.
England lost two wickets with the score on 101 with Paul Collingwood (28) hitting a thick edge to a Brett Lee rearer and Ricky Ponting taking an instinctive head-high catch at second slip, before Strauss followed in the next over.
Both Collingwood and Strauss had been earlier beneficiaries of dropped catches with Collingwood put down by wicketkeeper Adam Gilchrist on two and Strauss grassed in a straight-forward two-handed chance for Matthew Hayden in the gully on 41.
Opener Alastair Cook, who scored a century in the third Perth Test, was caught by Gilchrist off Lee for 11 in the morning session and Ian Bell was out for seven 20 minutes after lunch.
Stuart Clark trapped Bell leg before wicket but watched with dismay as Hayden put down an easy chance when Strauss was short of his first half-century of the series.
Strauss went hard after Clark and sliced to the fumbling Hayden.
Strauss went on to raise his 50 with a single off Warne. His painstaking half-century came up in 196 minutes off 130 balls with just one four.
Cook, who scored 116 in six and a half hours in the second innings in Perth, tried to avoid playing at a Lee seamer but got a bottom edge and was snapped up by Gilchrist chest-high. Lee had taken 2-36 off 13 overs at tea.
Australia regained the Ashes after winning the opening three Test matches and are trying to emulate Warwick Armstrong team's 5-0 Ashes sweep 85 years ago.
England 117 for 4 (Strauss 50, Collingwood 28; Lee 2 for 36, Clark 1 for 17, Warne 1 for 21) Vs Australia