At the break, Collingwood was still going strong on 109 and giving him company was Madhusudan 'Monty' Panesar on one.
Resuming at their overnight score of 246 for seven, England looked like folding up for around 270, but Collingwood frustrated the Indians, first with Matthew Hoggard and then with Steve Harmison, to take their team total past the 350 mark.
Collingwood put on 23 runs with Hoggard, with the latter frustrating the Indians for 52 minutes. Hoggard made 11 before the second new ball, claimed after 98.1 overs, saw his departure.
Sreesanth got one to pitch on the off stump and move slightly away from the right-hand batsman. Hoggard followed the ball and the edge went straight into the hands of the wicketkeeper M S Dhoni. England were 267 for eight at that time.
Collingwood was playing beautifully at the other end and, in Steve Harmison, he found an able ally. The two put on 60 runs with Harmison going after the Indian bowling, hitting Sreesanth for three consecutive fours just before the drinks break.
Not to be left behind, Collingwood also flicked Sreesanth to the mid-wicket boundary for another four and after that danced down the track to Harbhajan Singh to loft him for a straight six.
Harmison, however, went for a shot too many and after making 39, he stepped out of his crease to loft Harbhajan, but missed the ball and was easily stumped by Dhoni. He had seven fours in his 41-ball knock, with England on 327 for nine.
Collingwood, however, went from strength to strength as he lofted Harbhajan for another six to reach 99 and then reached his maiden Test century with a three to long on. He took 224 balls to reach his century that was studded with eight fours and three brilliant sixers.
He has put on 33 runs so far with Panesar who was defending his end very well and giving good company to the senior partner.