Beside Devdhar, Aditya Waghmode (88) and Yusuf Pathan (66) chipped in with half centuries to help Baroda post a mammoth 334 for nine in 50 overs after electing to bat.
Medium pacer Shrikant Mundhe's took a hat-trick but his effort went in vein as Maharashtra were bowled out for 284 in 48.5 overs at Saurashtra Cricket Association (SCA) Stadium at Khandheri.
Gujarat is the other team to qualify for the next round from West Zone.
Devdhar added 82 runs for the second wicket with Waghmode before getting out. Yusuf hammered four sixes and five fours for his 38-ball 66.
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For Maharashtra, Mundhe took a hat-trick in the last over but it was too late as Baroda had by then put up a formidable score.
Mundhe finished with four for 55, while Samad Fallah and Puskarraj Chavan took two wickets each.
When the visitors began their chase, medium pacer Irfan Pathan struck early, removing Harshad Khadiwale (0) and Rohit Motwani (31).
For Baroda, Meriwala took three for 61, while Irfan accounted for two wickets while giving away 41 runs.
Brief scores: Baroda 334/9 off 50 overs (Kedar Devdhar 103, Aditya Waghmode 88, Yusuf Pathan 66; Shrikant Mundhe 4- 55). Maharashtra 284 all out in 48.5 overs (Ankit Bawne 97, Nikhil Naik 78; Lukman Meriwala 3-61, Irfan Pathan 2-42).