England, at tea on the fourth day, were 221 for three in their second innings - still 62 runs of avoiding an innings defeat.
Vaughan was 91 not out and closing in on what would be his 17th Test hundred and fourth against India. Paul Collingwood was unbeaten on 13. India struck just eight balls after lunch.
Andrew Strauss had added just one to his interval score when he was out for 55. The left-hander, trying to force a Zaheer Khan outswinger off the backfoot through the offside, edged through to wicket-keeper Mahendra Singh Dhoni and England were 130 for two after a second-wicket stand of 81.
Vaughan, 36 not out at lunch, was lucky when a miscued hook against left-arm quick Khan just cleared Dhoni. But a square drive off Khan saw Vaughan complete a hundred-ball fifty with nine fours.
Pietersen dismissively pulled the first ball back from fast bowler Sreesanth through mid-on for four.
Sreesanth subsequently let loose an inswinging 'beamer' which just missed Pietersen's head. South African umpire Ian Howell signalled 'no-ball' as such deliveries are illegal under the Laws of Cricket.
The bowler raised his hand in apology and at the end of the over India captain Rahul Dravid, in a move to calm tempers, spoke to the batsmen.
It was the start of a dramatic four ball sequence for the South Africa born Pietersen. Next over left-arm quick Rudra Pratap Singh - who ran down past the batsman during an impassioned appeal - was convinced he had Pietersen caught behind, driving outside off-stump.
Dravid though spoke to his bowler and next ball Singh, from around the wicket and wide on the crease got a curving delivery to cut back sharply off the pitch and Pietersen, padding up, was lbw for 19 with Australian umpire Simon Taufel quickly raising his finger.
England were now 175 for three with their star batsman out cheaply before Sreesanth angered Vaughan with a full toss that the umpires did not deem worthy of censure this time.
Monday's first session was marred by the lastest of several unpleasant incidents this series when Sreesanth brushed shoulders with Vaughan and was spoken to by Howell.
By then England had lost opener Alastair Cook, lbw for the fourth successive time this series, Khan removing him for 17.
Vaughan, on 16, appeared fortunate to survive Anil Kumble's lbw appeal off the leg-spinner's first ball Monday before Strauss completed a 120-ball fifty.
India's first innings total of 481 saw five members of their top six score fifties, Sachin Tendulkar leading the way with 91. During his innings, Tendulkar became only the third batsman in history to score 11,000 Test runs.
Brief Scores (at tea, D-4):
England 198 and 221 for 3 (Vaughan 91 n o, Strauss 55, Cook 23; Zaheer 2 for 47, RP Singh 1 for 32) Vs India 481 (Tendulkar 91, Ganguly 79, Karthik 77, Jaffer 62, Laxman 54, Dravid 36; Panesar 4 for 101, Tremlett 3 for 80).