Jadhav scored 204 off 267 deliveries (29x4, 1x6), while Motwani hit a 239-ball 107 laced with nine fours to power Maharashtra to 616 for nine declared.
Sangram Dilp Atitkar (98) also chipped in with valuable runs.
At stumps on day two, Hyderabad were on 53 for no loss with TL Suman unbeaten on 28 and Akshath Reddy on 20.
Resuming on 337 for four, overnight batsmen Jadhav and Motwani completed their double century and hundred, respectively.
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Motwani then coupled with Atitkar to put on a solid 179 runs together for the sixth wicket.
M Ravi Kiran finished with four for 116, while Amol Shinde took three wickets.
Brief scores:
Maharashtra 1st innings: 616 for nine decl (Kedar Jadhav 204, Rohit Motwani 107; M Ravi Kiran 4/116).
Hyderabad 1st innings: 53 for no loss (TL Suman batting 28).