The world number five showed tremendous grit and concentration to beat back the challenge from strong contenders like Wang Zhiwei of China and South Korea's two-time Olympic champion and reigning world champion Jongoh to win the gold.
In fact both Zhiwei and Jongoh were eliminated in the race early on leaving only the Indian ace and unheralded Vietnamese Hoang Phuong Nguyen fighting for the gold.
It needed the last set of shots to decide the issue in favour of Rai. He shot 8.4 after the nervous Vietnamese was way off the mark to fire a poor 5.8 to win the gold.
He thus became only the second Indian pistol shooter to clinch an Asian Games title after Jaspal Rana and the fourth shooter overall after shotgun experts Randhir Singh in 1978 and Ronjan Sodhi in 2010.
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Rai said he badly wanted to win the gold here.
"I wanted to win this gold badly and was under a lot of pressure. The competition here was even more than in the Commonwealth Games or the World Championship. I am happy that I could fulfill my wish," he said.
National pistol coach Pavel Smirnov later praised Rai, describing him as a very strong character.
"He's very strong mentally. There had been lot of competitions this year leading into the Games, the CWG, the world championships. He's mentally strong and that's why he could do it," he said.