At stumps, Devdhar was unbeaten on 104 off 170 balls, while Waghmode faced 238 balls during his patient 87-run unconquered knock.
While Devdhar struck 12 boundaries, Waghmode laced his innings with 10 hits to the fence.
Apart from Devdhar and Waghmode, opener Saurabh Wakaskar made a 109-ball 50.
For Maharashtra, right-arm pacer Shrikant Mundhe picked up two wickets for 45 runs, while left-arm spinner Akshay Darekar accounted for the other Baroda batsman.
However, the start was far from rosy for Baroda as the visitors lost two quick wickets after being asked to bat.
Wakaskar and Waghmode then steadied Baroda's ship with a 70-run third wicket stand before Waghmode combined with Devdhar to take the visitors to a comfortable position at the end of the day.
Brief Scores:
Baroda: 256 for three in 90 overs (Kedar Devdhar 104 not out, Aditya Waghmode 87 not out; Shrikant Mundhe 2/45).