Marvin Williams posted 13 points and nine rebounds, while Michael Kidd- Gilchrist provided 10 points and 12 boards for the Hornets, who have won four straight games.
Kyle Lowry recorded 24 points, seven rebounds and seven assists to lead Toronto, which has dropped four straight on the heels of an 8-1 stretch.
After Terrence Ross' left corner 3-pointer clawed Toronto within 85-82 with 5:26 remaining, Charlotte scored seven of the next nine points to regain control.
Walker was fouled and sunk a pair of free throws before Lowry drove in for a layup. Henderson's layup and two foul shots preceded Bismack Biyombo splitting a pair from the charity stripe for a 92-84 Hornets advantage with 2:58 to play.
Patrick Patterson's tip-in whittled the deficit to 99-95 with 42.3 seconds left. Walker, however, nailed a back-breaking, step-back left wing jumper at the other end with the shot clock winding down to essentially seal the outcome.
Earlier, Charlotte built a 31-23 margin following a quarter of play, but 3- pointers by Greivis Vasquez and Tyler Hansbrough in the early stages of the second highlighted an 8-0 spurt, which tied the game at 31-31.
Toronto led 52-50 at the break.
Henderson, though, netted the first four and the final four points of a 14-1 Charlotte surge to start the second half.
The Hornets took a 75-66 cushion into the fourth.
It was Walker's 42nd career game with 25-or-more points. He had nine points in the fourth quarter and also supplied eight assists and seven boards overall ... The Raptors had their five-game home winning streak snapped ... Toronto's four-game losing streak is its longest since falling five consecutive times from Nov. 26-Dec. 6, 2013.