The French forward, 26, joins on an initial loan deal for a fee of €5 million – with an obligation to make the transfer permanent for €15m should certain sporting targets be met.
The agreement also includes performance-related payments, worth up to an additional €3m, dependent on achievements on the part of both the player and club.
Defrel has signed a five-year contract with the Giallorossi that runs until 30 June 2022.
“It means a lot to me to be able to play for Roma,” Defrel said. “I’m going to be part of a very strong group, one of the best teams in Italy.
"I’m delighted to be here and I will give my all for the team.”
Defrel spent the last two seasons with Sassuolo, scoring 23 goals in 73 games for the Serie A side and helping them quality for the Europa League at the end of the 2015-16 campaign.
“I’m really happy to finally add Gregoire to our squad." the club's sporting director, Monchi, said. "He was a priority for us because he is exactly the type of forward we were looking for.
"He can play in three different positions, he’s quick, he plays for the team, he gives us depth and he has a great nose for goal.”
Defrel came through Parma’s academy system, and has represented both Foggia and Cesena during his senior professional career to date.
He will fly out immediately to join his new teammates on their ongoing tour of the United States.
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