Resuming on 287 for three, overnight batsman Rao, starting on 68, went on to score a 277-ball 177 laced with 22 fours and two sixes to put the hosts in a strong position.
The other overnight batsman -- centurion Parthiv Patel -- however failed to add any run to his last night's score of 109.
Rao played a responsible innings and also put on a solid 93-run stand for the seventh wicket with Jesal Karia, who chipped in with crucial 39 runs.
For Odisha, Jayanta Behera took three for 111.
Odisha began well with Girija Rout (39) putting on 111 with Natraj Behera for the opening wicket before falling lbw to Jasprit Bumrah off the last ball of the day.
Odisha still trail Gujarat by 368 runs with nine wickets in hand.
At stumps, Natraj was batting on 64 and he remains on course for his fourth century in as many innings.
Brief scores:
Gujarat 1st innings: 479 for 8 dec (Parthiv Patel 109, Venugopal Rao 177; Jayanta Behera 3/111).
Odisha 1st innings: 111 for one in 41 overs (Natraj Behera batting 64).
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