Pietersen's innings started doggedly, and he can consider himself fortunate to have survived a debated catch on 49, but by the declaration on 474 for eight, he was at his swaggering best.
In all Pietersen had batted for over eight hours, hitting 21 fours and a six and passing 6,000 Test runs in the process.
India, meanwhile, survived a tricky five overs at the close to reach 17 without loss.
They had toiled for large periods without their stricken spearhead Zaheer Khan, absent with a hamstring strain, though there was some joy for Praveen Kumar.
The swing bowler twice took two wickets in an over to check English momentum and closed with five for 106 to join Pietersen on the famous honours board.
England resumed this morning on 127 for two, with Jonathan Trott driving the first boundary of the day off Praveen and Pietersen immediately more assured than during his skittish 22-run cameo on Thursday.
He got going with two punchy fours through mid-on and was soon collecting regular singles.
Trott looked typically solid and it was a surprise to see Praveen beat the bat and trap him lbw on the back foot for 70.
India installed a leg slip for Praveen and it looked like a master stroke when Pietersen, one short of his half-century, turned one round his pad to the waiting Rahul Dravid.
Having dropped Trott on eight yesterday, the 38-year-old got down well this time but could not be certain of the catch and the umpires sent the decision upstairs.
As so often happens, replays gave the batsman the benefit of the doubt and Pietersen survived, though he can feel fortunate to have done so.
His 50 followed off 134 deliveries, the longest Pietersen has ever taken to reach that mark.
Harbhajan Singh was bowling to some defensive fields but was struggling to contain England, Pietersen timing a four over mid-off and Ian Bell scoring briskly on both sides of the wicket.
Pietersen then clubbed an aggressive, though not entirely impressive, stroke off Ishant Sharma for two to bring up the 200.
