Kohli, who is set to become the Indian batsman with most double tons, remained unbeaten on 194 from 286 balls, his marathon innings lasting more than six hours, laced with 28 fours.
Ravindra Jadeja, promoted to bat at No. 6, was batting with him on 25 from 59 deliveries as the pair shared an unbroken 97-run stand for the fifth wicket.
This was after Kohli and Ajinkya Rahane had associated for a 178-run partnership before the India vice-captain departed for 59 off 168 deliveries (8x4), Keshav Maharaj having him caught behind by 'keeper Quinton de Kock.
But there was no stopping Indian batsmen from scoring runs as Jadeja, playing in Hanuma Vihari's batting position, milked the tired South African bowlers for easy runs while Kohli upped the ante to take Maharaj for two boundaries in an over.
Earlier, Kohli scored a brilliant hundred as he, along with Rahane, took the hosts to a commanding position. At Lunch, India were sitting in the driver's seat at 356/3.
Starting the day at 273/3, both the overnight batsmen played out the first hour rather cautiously as the Proteas pacers kept bowling on probing lines and tested the techniques of the Indians with the second new ball at the Maharashtra Cricket Association (MCA) Stadium. <br> <br>During the course of his innings, Kohli also went past Dilip Vengsarkar's tally of 6,868 runs to climb to the seventh position in the list of players with most runs for India in the longest format.
The Indian team amassed 83 runs in the session without losing any wicket in the morning session. <br> <br>Earlier on Day 1, Mayank Agarwal (108) had scored a brilliant century and was ably supported by Cheteshwar Pujara (58) as India reached 273/3 when umpires called for early stumps because of bad light. <br> <br>Brief scores: India 473/4 (Virat Kohli 194 batting, Mayank Agarwal 108, Ajinkya Rahane 59, Cheteshwar Pujara 58; Kagiso Rabada 3/93) <br> <br>--IANS<br>dm/aak/in