Maharashtra ended their Ranji Trophy group league engagements as table toppers with 35 points from eight games.
Chasing 344 for victory, Assam required another 250 runs on the fourth day with six wickets remaining.
However, the hosts could manage to score 215 in their second innings with left-arm spinner Akshay Darekar picking up four for 84 while medium pacer Shrikant Mundhe finishing with two for 28.
This was Maharashtra's fourth outright win this season.
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Syed Mohammad (11) too departed in quick succession, caught and bowled by Darekar.
Kunal Saikia and other overnight batsman Dheeraj Jadhav batted cautiously to raise a 52-run partnership for the seventh wicket before Darekar returned to send back the former for 32.
Jadhav, starting on 37, however, went on to complete his half-century even as wickets kept tumbling at the other end.
Jadhav departed after making a fighting 193-ball 61, laced with five fours.
Brief Scores:
Maharashtra: 361 and 134 beat Assam 152 and 215 in 72.4 overs (Dheeraj Jadhav 61, Abu Nechim Ahmed 46; Akshay Darekar 4/84).
Points: Maharashtra 6, Assam 0.