The defending Shield champions were cruising at 2-261 chasing 295 for victory, before Doolan's dismissal sparked a stunning capitulation where Tasmania lost 6-23.
However, a brave six down the ground off Nathan Lyon from Clive Rose playing just his second first-class game helped the Tigers get within four of the win, before the 24-year-old tailender finished the job with another slog down the ground in the 97th over off Steve O'Keefe.
Rose's 13 not out was crucial in the two-wicket win after big-hitter Luke Butterworth was controversially stumped off Lyon to leave Tasmania eight down with 11 still needed.
But Doolan was the difference with 132 from 194 balls, a clear man-of-the-match after also posting a half century in the first innings.
The Tigers resumed at 1-18 on day four with stoic opener Ed Cowan already back in the shed, and the Blues appeared to have the visitors on toast.
Despite spinners Lyon (3-88) and O'Keefe (3-53) rallying late, it was a disappointing performance from a NSW side trying to turn around fortunates this season and bring home a title.
The Blues were powerless to stop Doolan once he got on a roll, as he shared in consecutive 100-run stands with Ben Dunk (67) and Jonathan Wells (57).
Unfortunately for NSW captain Michael Clarke, the flow of wickets came a little too late.
While Doolan put himself in the frame for a Test call-up, NSW's high-profile bowling attack didn't earn too many favours.
Although Lyon - who has Victorian legspinner Fawad Ahmed hot on his tail ahead of the first Ashes Test in Brisbane - finished well.
Pace bowler Josh Hazlewood (1-45) never looked like causing a breakthrough on the final day.
Hazlewood, who is part of Australia's plans for the Ashes, also struggled to fire in the domestic one-day tournament.
Doolan was being talked about for a Test call-up last summer, and is a realistic chance again for the coming Ashes, with at least one spot in the Australian batting line-up there for the taking.
It would seem his Tigers' teammate George Bailey has a stranglehold on the vacant No.6 spot for the first Test in Brisbane, but Doolan's sixth first-class ton in difficult batting conditions will ensure he's well and truly in the conversation for a Test debut.
Doolan scored a fine 56 in the first innings and has been the standout batsman for the game on a slow Blacktown pitch, even overshadowing Michael Clarke, who made 88 in NSW's first dig.
Tasmania had a clear plan to attack their target of 295 when they resumed on day four, with Doolan executing the game-plan perfectly until he was ultimately out lbw to one that stayed low from O'Keefe.
Turning 28 later this month, Doolan played smart but elegant cricket, stroking 18 fours and a six.
Launceston-born Doolan will have another important chance to impress selectors on his home-State pitch in Hobart, when he lines-up for Australia A against England.
A big hundred against the Ashes opposition on the eve of the series starting will make a big statement.