Pietersen, under fire for his unproductive batting in England's troubled series, curbed his natural attacking instincts to keep the pressing Australians at bay before a crowd of 91,092, the highest single-day attendance for any Test match.
Pietersen went to stumps unbeaten on a fighting 67 off 152 balls, with Tim Bresnan not out one in England's 226 for six. In doing so Pietersen passed Geoff Boycott as the fourth all-time England run-getter.
The subdued Pietersen had some luck along the way and denied the impressive Ryan Harris both times, as England were pinned down by a disciplined Australian bowling attack on a slow scoring day at the Melbourne Cricket Ground.
Pietersen, who took 12 balls to get off the mark, had some good fortune on six when he was caught by fielding substitute Nathan Coulter-Nile at deep backward square leg off Harris.
But Coulter-Nile was unable to stay within the field of play in taking the catch, staggering over the boundary marker, and Pietersen was awarded a six instead.
He had a second "life" on 41 when George Bailey had two goes in a fumbling attempt at a catch off Harris at mid-wicket.
Pietersen, who thrills and frustrates in equal measure with his prodigious batting skills, anchored the tourists' innings.
Harris, who was superb leading the Australian attack, ended a threatening 67-run partnership when he got Ian Bell to nick an outswinger to Brad Haddin for 27 in the 73rd over.
Bell's obdurate innings came off 98 balls in just over two hours, with just one four.
During his innings Bell joined Michael Clarke in passing 1,000 runs for the calendar year.
Perth Test centurion Ben Stokes fell late in the day when he edged to Shane Watson at slip off Mitchell Johnson for 14. He he was followed by Jonny Bairstow, replacing Matt Prior but bowled by a Johnson snorter for 10.
The Australians' tight bowling line restricted the English scoring and extracted the wickets of opener Michael Carberry and Joe Root in the middle session.
Carberry shouldered arms and lost his off-stump to Watson for 38 to waste another good start.
Carberry, who was dropped in the slips on two, had done all the hard work but was beaten by terrific movement off the pitch from Watson in the 34th over of the innings.
It was the third time all-rounder Watson had snared Carberry's wicket in this series. In nine Test innings he has been out six times between 30 and 43.
Harris removed Root with an outswinger, enticing an edge to Haddin for 24 in the 43rd over.
Root, like Carberry, had established himself in an 82-ball stay but Harris's perseverance won through in a patient bowling performance.
But Watson's well-catalogued injury jinx struck again when he was unable to complete his seventh over late in the middle session and left the ground for treatment for a right groin problem. He returned to the field late in the day to take the catch to dismiss Stokes.
Australian captain Michael Clarke -- with an unassailable 3-0 lead in the five-match series and the Ashes already recovered -- won the toss and sent the troubled tourists in to bat under overcast skies.
England got to first-hour drinks without losing a wicket but lost skipper Alastair Cook three overs later when he nibbled at Peter Siddle and was caught by Clarke at second slip for 27.
In the 19 tosses Clarke has had as Australia skipper it was only the fourth time he has put the opposing team into bat.
England dropped vice-captain Prior and named Bairstow as wicketkeeper, while Monty Panesar was chosen as the specialist spinner following the shock mid-series retirement of Graeme Swann.
In contrast Australia named an unchanged side for the fourth consecutive Test in the series.