Wayne had 64 receptions for 779 yards and two touchdowns last season for the Indianapolis Colts, but the team announced in March it would not be re-signing the 14-year veteran whom they selected in the first round of the 2001 draft.
Coincidentally, Wayne's final game as a member of the Colts happened to be against the Patriots, when he was not targeted once in the AFC Championship Game in January, a game perhaps now more remembered as being the start of Deflategate.
"I'm happy for him," said kicker Adam Vinatieri, who left New England to sign with the Colts in 2006. "I know he wanted to play football. He's a great competitor and great athlete. He's a great receiver. He's going to make that team better. It'll be interesting to see him come here [in Week 6], having him have a different jersey on."
Wayne fits a need on the Patriots as the team has several question marks among its receiving corps due to injuries.
Julian Edelman has been out since Aug. 2 with a lower leg injury, though he is still expected to be ready for Week 1. Brandon LaFell remains on the physically unable to perform list and Aaron Dobson has been sidelined by a reported hamstring injury the last two weeks.
Patriots coach Bill Belichick has long spoke with admiration about the 36-year-old Wayne.
"He's certainly had a great career and has done a lot of things for the Colt organization, primarily playing on the left but then in more recent years being moved around to playing on the right and also in some slot situations," Belichick said Monday on WEEI. "I think he has a lot of versatility and obviously he has a lot of experience, so we'll just have to see how it goes."
Wayne's flexibility to play outside or in the slot fits the Patriots' mold, as the team generally likes to move its receivers around liberally.
Based on history, however, age may catch up with Wayne, who will turn 37 in November. There have only been 10 seasons in NFL history in which a player 37 or older caught at least 50 passes, and half of those seasons belong to Jerry Rice.
ESPN.com's Mike Wells and Mike Reiss contributed to this report.