Curry overcame a slow start to finish with a season-high 43 points, 32 of them coming in the second half.
Curry, a Charlotte native who burst on the national scene while playing at nearby Davidson College, scored 19 points in the fourth quarter, including a 27-footer with a hand in his face to cut the Bobcats' lead to 111-109 with 11 seconds left.
But the Warriors (12-10) couldn't contain Walker, and the point guard hit four free throws in the final 11 seconds to seal the victory.
Gerald Henderson had 24 points and Josh McRoberts had 11 points and 10 rebounds for the Bobcats (10-11), who won their second straight game.
While Curry was putting on a show, Walker did his best to match him in a duel of high-octane point guards.
Walker scored 15 points in the fourth quarter and finished 10 of 18 from the field and 9 of 11 from the foul line. He also had five assists.
Curry was 3 of 11 in the first half, but got hot late in the third quarter and finished 14 of 32 from the field against a Bobcats team that hadn't allowed 100 points in 13 straight games. He was only 5 of 16 from 3-point range, but did some damage at the free throw line where he was 10 of 12.
Curry also had nine assists.
The Bobcats led 53-41 at the half behind 14 points from Henderson, who was 7 of 10 from the field, scoring most of his points in the low post. The Warriors struggled from the field early, shooting 1 of 12 from 3-point range.
Curry, who led Davidson to the brink of the Final Four as a sophomore, came in with a career average of 25.3 points against his hometown team while shooting 62 percent from 3-point land.
The Warriors never led, but tied the game at 88-all on a pair of free throws by Curry.
But Ramon Sessions scored on a pair of drives and Ben Gordon knocked down a 3-pointer to quickly push the lead back to seven with 6:50 left in the game. Walker hit a 3-pointer and a fall away in the lane to help stretch the lead to 11.
Warriors coach Mark Jackson said before the game that Curry's play has been "spectacular" this season.
"He's been playing at a whole different level," Jackson said. "He's playing and acting like he's the best player on the floor night-in-and-night-out, carrying us down the stretch, making plays, choosing when to take over offensively and he knows when to facilitate."
"You see his scoring and you fall in love with his jump shot. He's a guy that's among the league leaders in assists also. He's playing at a different level. He's getting to the level of the baddest man on the planet. It's really fun to see. It takes everyone else to another level."