A world-record crowd of 91,092 saw Australia captain Michael Clarke make the surprising decision to bowl first in overcast conditions.
And without Pietersen's resistance, helped by some missed chances, Australia could have more emphatically claimed the honours for the opening day.
Pietersen's unbeaten 67 off 152 balls has at least given the tourists, who trail three-nil in the five-match series, some hope of making a game of it.
Australia's bowling attack was unbalanced on Thursday by the groin injury to star allrounder Shane Watson, who limped off midway through his seventh over and returned later in the day to take a catch at first slip.
Tailender Tim Bresnan survived a scary late burst from Mitchell Johnson (2-59) with the second new ball to be one not out.
England captain Alastair Cook (27) shared an opening stand of 48 with Michael Carberry.
Dropped at third slip on two, Carberry was bowled by an inswinger from Watson on 38.
It was time for the main event after Joe Root was out for 24 at 3-106 as the right-hander was caught behind off the bowling of Ryan Harris.
Heavily criticised for his shot selection during a modest series and labelled a mug by Geoff Boycott, Pietersen put his head down in a patient 67-run stand with Ian Bell (27).
Bell was the victim of a leg cutter from Harris who claimed 2-32 off 20 overs.
Pietersen was caught at fine leg on six before sub fielder Nathan Coulter-Nile stumbled over the boundary and the batsman had a second life on 41 when George Bailey dropped a tough chance at mid-wicket.
Harris looked unimpressed as a third chance went begging off his bowling.
Pietersen was booed to the crease and booed for his half-century milestone.
On 45 he had a close encounter with a fly and held up play for several minutes, appearing to dry-retch. The crowd showed no sympathy, clapping impatiently.
Johnson removed Ben Stokes (14) and Jonny Bairstow (10) with the second new ball in a fiery spell that included Pietersen top-edging a pull shot for six.
Pietersen on 63 became England's fourth-leading run-scorer, fittingly overtaking Boycott (8114).
Clarke's decision to bowl was the first time Australia had inserted England since Ricky Ponting's ill-fated move at Edgbaston in 2005.
"I can't believe I'm saying this. We're going to have a bowl first," Clarke said.
"There's enough moisture and grass on the wicket."
ENGLAND FIRST INNINGS
A COOK c Clarke b Siddle 27 (47)
M CARBERRY b Watson 38 (103)
J ROOT c Haddin b Harris 24 (82)
K PIETERSEN not out 67 (152)
I BELL c Haddin b Harris 27 (98)
B STOKES c Watson b Johnson 14 (23)
J BAIRSTOW b Johnson 10 (17)
T BRESNAN not out 1 (13)
Sundries (10b 6lb 1w 1nb) 18
Six wickets for 226
Fall: 48 (Cook), 96 (Carberry), 106 (Root), 173 (Bell), 202 (Stokes), 216 (Bairstow).
Bowling: R Harris 20-8-32-2, M Johnson 20-2-59-2 (1w), P Siddle 22-7-48-1 (1nb), N Lyon 20.2-3-60-0, S Watson 6.4-2-11-1.
Batting time: 391 mins. Overs: 89.
Umpires: Aleem Dar (PAK), Kumar Dharmasena (SRL).