The German, driving the number 19 works Porsche he shared with New Zealand's Earl Bamber and Briton Nick Tandy, took the chequered flag for the marque's first win at the Sarthe circuit since 1998.
It was Porsche's 17th Le Mans triumph, extending the team’s own record.
The number 17 Porsche of Australian Mark Webber, New Zealand's Brendon Hartley and Germany's Timo Bernhard finished second, while Audi's defending champions Andre Lotterer, Benoit Treluyer and Marcel Faessler completed the podium places in the 83rd edition of the endurance race.
“I'm speechless right now, to be honest,” said Hulkenberg before lifting the heavy trophy with the help of his team-mates.
“It's amazing to come here, first attempt. Super happy...we wrote history today,” added the 27-year-old, the first active F1 driver to win since Britain's Johnny Herbert in 1991.
“We couldn't expect such a thing,” said the German, who arrived in Le Mans straight from the Canadian Grand Prix and will be heading to Austria for next weekend's race after a few days off.
The winning trio were the least experienced of the three Porsche works crews, with Hulkenberg completely unfamiliar with Le Mans until testing two weeks ago.
Tandy, the only one of the three with prior Le Mans experience, became the 30th British winner of the event.
“I couldn't think of two guys I'd rather share the car with,” said the Englishman. “I could retire from racing tomorrow and look back on today and I am sure I would be happy for the rest of my life.”
Bamber was only the third New Zealander, following in the footsteps of Formula One drivers Bruce McLaren and Chris Amon in 1966, to win Le Mans.
Audi had won 13 of the last 15 editions but Porsche, which returned with a full factory effort last year, had looked dangerous from the moment the team swept the top three grid places in qualifying.
WHERE IT WENT WRONG FOR AUDI
There had been little to separate the two Volkswagen stable mates going into the night but things started to unwind for Audi after daybreak.
Fassler had to pit when a large part of bodywork flew off without warning, costing seven minutes for repairs. The number nine and eight Audis also suffered mechanical problems.
Webber led at the quarter distance but fell back when Hartley collected a one minute 'stop and go' penalty for overtaking through a slow zone imposed around the Mulsanne corner during the third safety car interlude.
The safety cars came out for a fourth time around the 17 hour mark when an Aston Martin crashed heavily.
The safety cars, three of them to cope with the long Le Mans lap, made their first appearance after the first hour when a three car collision dumped oil on the track at the first chicane.
There was a much longer safety car period at the end of the third hour, when Frenchman Loic Duval spun and hit the barriers in the number eight Audi at the Indianapolis corner.
Denmark's retired nine times winner Tom Kristensen had waved the 83rd edition of the race away in bright sunshine on Saturday, watched by a crowd of around 250,000 spectators enjoying a festival atmosphere. -Reuters
24 HOURS OF LE MANS: RESULTS
1. Hulkenberg-Bamber-Tandy (GER-NZL-GBR/Porsche 919 Hybrid) 395 laps
2. Webber-Bernhard-Hartley (AUS-GER-NZL/Porsche 919 Hybrid) at 1 lap
3. Treluyer-Fassler-Lotterer (FRA-SUI-GER/Audi R18 e-tron quattro) 2 laps
4. Jarvis-Duval-Di Grassi (GBR-FRA-BRA/Audi R18 e-tron quattro) 3 laps
5. Dumas-Jani-Lieb (FRA-SUI-GER/Porsche 919 Hybrid) 4 laps
6. Wurz-Sarrazin-Conway (AUT-FRA-GBR/Toyota TS040 Hybrid) 8 laps
7. Albuquerque-Bonanomi-Rast (POR-ITA-GER/Audi R18 e-tron quattro) 8 laps
8. Davidson-Buemi-Nakajima (GBR-SUI-JPN/Toyota TS040 Hybrid) 9 laps
9. Lapierre-Bradley-Howson (FRA-GBR-GBR/Oreca-Nissan) 37 laps
10. Evans-Turvey-Dolan (NZL-GBR-GBR/Gibson-Nissan) 37 laps
RACE HIGHLIGHTS VIDEO:
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Original source: Le Mans: Full story, pics & video