It was a huge boost to the 6-1 Walker's confidence, and the second-year pro has been a different player throughout the preseason.
He scored a career-high 30 points, and carried the Bobcats through three quarters to put them in a position to win at the end.
They ultimately held on when Augustin missed a 3-point attempt from the corner at the final buzzer that would have won it for the Pacers.
"I feel like my coach believes in me; I can go out there and be as confident as I can be," Walker said. "It's all about trust. It's all about confidence. When I'm confident, my teammates are confident and we just make things happen. So my coach having trust in me is definitely a huge deal."
The victory gave new coach Mike Dunlap a victory in his debut and snapped the Bobcats' 23-game losing streak at the end of last season. The Bobcats were an NBA-record worst 7-59 last season under Paul Silas.
"Man, it was a huge win," Walker said. "We got that monkey off our back early. I don't think we went into the game thinking about the losing streak. We just went into the game thinking about all the hard work we put in this offseason to get to this point. We just fought hard. We stayed together through the tough times of the game and we won."
Dunlap wasn't about to downplay the significance of the win.
"The most important thing was to kill the elephant," Dunlap said. "Our elephant was the losing streak, and to get that off everybody's back in this entire organization from the city to whatever, it's just one of those marks you want to clean off the board. We're happy we got away from that. And away from that was some gritty play tonight."
Walker, whose previous career high was 23 against Golden State last Jan. 14, finished 10-for-21 from the field and 9-of -10 from the line. He also had five rebounds, three assists and one steal in 33 minutes, against just one turnover.
He had 16 points in the first half, and then erupted for 12 in the third quarter when the Bobcats came back from a 43-39 halftime deficit to lead by as many as eight.
"That's what he's capable of doing," teammate Ramon Sessions said. "When he's playing his game, you're going to see games like that."
"Coach has told me to be aggressive and stay aggressive," Walker said. "Early in the game I think I took two shots and stopped, and he told me whenever I get to the free-throw line or got a mid-range jumper to keep on taking it. He told me don't stop taking it. I was just fortunate enough to be making them tonight."
The Bobcats also got 18 points from Gerald Henderson, 11 from Sessions and 10 from Ben Gordon.
Tyler Hansbrough and Lance Stephenson came off the bench to lead the Pacers with 15 points apiece. David West scored 16 but was 7-of-17 from the field, as the Bobcats played a variety of zones to limit his effectiveness. West had scored 25 points in the Pacers' 90-88 season-opening victory at Toronto on Wednesday night.
The Pacers were without last year's leading scorer, Danny Granger, who continues to be sidelined by a sore left knee.
Pacers coach Frank Vogel said Granger "continues to get second opinions" and that there is no timetable for Granger's return.
The Pacers had won seven straight road games dating to last season before Friday night, so they clearly had confidence going down the stretch. But a 24-second shot-clock violation in the final minute cost them their first chance to take the lead, and then Augustin missed at the buzzer after Walker had missed a jumper for the Bobcats with 17 seconds left.
"We turned the ball over too much at the end," Indiana's Roy Hibbert said. "We had two or three turnovers that cost us. It's disappointing, but it's only the second game of the season and we're playing short-handed right now. We can't get too high or too low over one game. We just have to learn from this and move on."
Charlotte will play at Dallas on Saturday, while Indiana will return home for its home opener against Sacramento.