At the break, de Villiers having completed his fifth Test century in the last over before lunch was unbeaten on 102, while Kallis was batting on 97, just three short of his century which will take him past Don Bradman in the most century makers list.
South Africa resuming on 223 for four under overcast conditions saw the two overnight batsmen batting sensibly pushing the scoreboard along as visitors looked to bat India out of the match.
AB de Villiers completed his fifth century and faced 174 balls which included 11 boundaries and a five in his century.
He along with Jacques Kallis added 83 runs in 29 overs in the two-hour morning session today to swell the South African lead.
India took the new ball after 81.2 overs, though, the new ball bowlers Sreesanth and R P Singh troubled the South African duo, the breakthrough was did not come as Kallis and de Villiers dug in deep to take South Africa to a mammoth score swelling their unbeaten stand to a new record for the fifth wicket for South Africa against India.
Both played the waiting game to perfection with Irfan Pathan and Harbhajan Singh who opened the bowling for India on the second day bowled a tight line and length.
Infact, Irfan Pathan in his first spell went for just four runs in his four overs, two of those being maidens.
However, as the skies cleared and the sun came out, both the batsmen grew in confidence and played some pleasing shots on both sides of the wicket to swell the South African total and the lead.
Both of them showed tremendous application to the job at hand, something the Indian batsmen had failed to do yesterday when Dale Steyn had ripped through the batting line-up to dismiss the hosts for 76 in the first session itself as the duo slowly but surely ensured that India were batted out of the game.
The duo during their partnership also created a record for the fifth wicket partnership for South Africa against India when the partnership reached 165 runs beating the previous best of 164 runs between Jacques Kallis and Lance Klusener made in Bangalore in 2000.
The new ball which was taken after 81.2 overs did put the South Africans in some trouble as both Sreesanth and R P Singh troubled the South African pair with a few close leg before calls going the batsmen's way.
But Kallis and de Villers managed to see through the new ball till lunch to put South Africa in a position where they have the hosts on the mat and only the final nail in the coffin is remaining.