At stumps, Maharashtra were 376 for seven, 14 runs ahead of Baroda's first innings total of 362 all out.
Khadiwale, resuming at the personal score of 69, went on to make 168 off 276 deliveries during which he hit 19 boundaries and one six.
Khadiwale got the perfect support from his skipper Motwani as the duo shared 166 runs for the fifth wicket before the former was caught off his own bowling by left-arm spinner Bharghav Bhatt.
Motwani too became Bhatt's victim but not before taking Maharashtra to safety. He hit 11 fours during his 239-ball knock.
For Baroda Bhatt scalped three wickets for 116 runs while Gagandeep Singh picked up two giving away 95 runs.
With only a day remaining, the match is heading for a draw and Maharashtra would be more than happy to pocket three points from the encounter by virtue of first innings lead.
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Brief Scores:
Baroda: 362 all out in 130.4 overs (Aditya Waghmode 113, Kedar Devdhar 104; Shrikant Mundhe 4/72).
Maharashtra: 376 for seven in 135 overs (Harshad Khadiwale 168, Rohit Motwani 91; Bharghav Bhatt 3/116).