Defending champion Zou Kai had been the favourite to win the gold medal as China had won every Olympic and world title on the apparatus since 2008 but he was easily surpassed by a rival who showed no fear as he pulled off three electrifying back-to-back release manoeuvres to whip the crowd into a frenzy.
Zonderland pulled off a 'Cassina' a 'Kovacs' and a 'Kolman' and his gamble paid off as he triumphed with 16.533 points to end the Netherlands' 84-year wait for an Olympic gymnastics gold.
Germany's Fabian Hambuechen, who thought he had bagged the title with his high-flying performance, finished with silver on 16.400 with Zou third on 16.366.
"I dreamed about it for so long. This routine was a lot of risk," Zonderland told reporters. "I still can't believe it. It's unique to be in a Olympic final if you're a Dutch gymnast, but winning the gold is bizarre.
"I worked so long to achieve a result like this. This is amazing."
Like Zonderland, Zou also pulled off a difficult, albeit less crowd-pleasing routine that had a 7.900 difficulty score.
But a tiny step back on his double-twisting double-straight-back somersault dismount made the difference between gold and bronze.
"I'm very satisfied with these results. I've won two golds and one bronze medal (at these Games). I can't win them all," he said laughing after taking his overall Olympic haul to five golds and a bronze.
With the Olympics over, he quickly turned his focus to a more difficult ordeal ahead of him.
"I'd like to propose to my girlfriend, maybe by the end of the year. I'm trying to think of a way," he said with a wink.
Hambuechen is no stranger to getting proposals himself, with one female fan holding up a banner imploring "Marry Me Fabbi-now!" and she bounced up and down on her seat as Hambuechen soared from one spectacular release-and-catch move to another - pulling off four in total.
The 2007 world champion let out a roar as soon as he landed and swaggered around the arena with out-stretched arms as he lapped up the deafening chants of "Fabbi-Fabbi-Fabbi".
Five minutes later, the 24-year-old had the smile wiped off his face and he glumly slumped into a chair as Zonderland took over the spotlight with a routine that was accompanied by a 13,000-strong chorus of "oohs" and "aahhs" from start to finish.
However, it soon dawned on Hambuechen, who made his Olympic debut as a bespectacled, cocky teenager in 2004, that a silver medal was better than nothing.
"I cannot describe this feeling, it's just amazing. After such a long time and all the heavy training it's great to get a silver medal," grinned Hambuechen, who won bronze in Beijing.
"In Athens I was 16, everything was new and exciting. In Beijing I was the world champion and everyone expected me to get the gold, the pressure was intense.
"Now in London I was happy to recover and perform well after a big injury last year. I'm very happy."
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