Maloney, 25, has signed a three year deal with the Tricolours, commencing in 2013.
Maloney is likely to be a substitute for Todd Carney who was released by the Roosters in September and later signed for Cronulla.
Sydney Roosters recruitment manager Peter O’Sullivan said: “2011 was a breakthrough year for James and we see him taking his game to the next level at the Roosters, forming a strong long-term partnership in the halves with Mitchell Pearce.”
Roosters Coach Brian Smith added: “James has a style of play that will complement the Roosters and has a high goal kicking percentage as well.
“He will be in his prime across the seasons he has signed with us and we look forward to welcoming James to the Roosters in 2013.”