It was the first meeting between the teams since last season's Eastern Conference playoffs, won by the Cavaliers in six games.
The Cavaliers led 71-56 with 55.9 seconds left in the third quarter before the Wizards took control. They scored the final four points of the period and then held a 33-18 edge in the fourth quarter.
Roger Mason added 11 points for the Wizards (1-2).
Anderson Varejao scored 14 points, Larry Hughes 13, and Daniel Gibson, Zydrunas Ilgauskas and Shannon Brown 10 apiece for the Cavaliers (1-2).
James, who sat out the Cavaliers' game against Boston on Friday night for precautionary reasons, had 12 points, seven rebounds and four assists.
The Wizards' Gilbert Arenas didn't get his first basket until 5 minutes were left in the third quarter. He finished with three points and three assists.
- The Cavaliers waived power forward Brandon Hunter before the game, cutting the roster to 17 players.
- Wizards swingman Jarvis Hayes, who missed all but 21 games last year with a knee injury, turned his ankle in the second quarter.