Tampa Bay, in exchange, will receive a sixth-round pick in this year's draft.
Williams was selected by the Bucs in the fourth round of the 2010 draft out of Syracuse, where he was suspended by Marrone for the 2008 season for off-the- field issues. The 6-foot-2 wideout returned to the team the next year before quitting midseason.
"With regard to our time at Syracuse, I feel that is in the past for both of us," said Marrone on the Bills' website. "Mike has an opportunity to get a fresh start to his career here in his hometown and regain his form as a productive player in the National Football League."
The Buffalo native had a productive first three years in Tampa Bay before a hamstring injury limited him to 22 catches and 216 yards last year.
For his career, Williams has caught 215 passes for 2,947 yards and 25 touchdowns, 11 coming his rookie year.
"We thank Mike for his contributions to the Buccaneers over the last four seasons," said Buccaneers general manager Jason Licht. "At this time we felt this was best for both sides and we wish Mike well going forward."
The trade comes a week after Williams was involved in an incident that ended with him being treated at a hospital for a stab wound to his thigh. His brother, Eric Baylor, was charged with aggravated battery domestic violence.
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