Four-time NBA Most Valuable Player James finished with 20 points, 12 assists and 10 rebounds to help the Cavs post their 18th straight home win.
Cleveland pulled four games ahead of the second-placed Bulls in the Central Division with five games to play.
J.R. Smith made half of Cleveland’s whopping 16 three-pointers and finished with 24 points.
Kyrie Irving added 27 points, including a stunning shot from beyond halfcourt as the shot-clock ran down late in the third quarter.
The shot — from more than 50 feet out — swished through the net, part of a 10-0 Cleveland scoring burst that extended their lead to 75-60.
Mike Dunleavy led Chicago with 24 points, while Aaron Brooks added 17 and Jimmy Butler chipped in 16 in the Bulls’ second defeat in three games.
Among Cleveland’s 10 three-pointers in the first half were impressive buzzer-beaters by Irving and Smith to end the first and second quarters, which helped the hosts take a 54-45 lead into halftime.
The Bulls narrowed the gap to 79-71 going into the fourth quarter, and pulled within five at 92-87 with just over three minutes to play.
Two of their next three possessions ended in turnovers, and Nikola Mirotic missed a three-pointer on the other.