The 26-year-old pulled off the most difficult release combination - a Cassina to Kovacs to Kolman - in a spectacular performance to score 16.533 and claim his first Games title.
Defending Olympic champion Zou Kai of China produced a near-perfect routine with a huge difficulty tariff but could only finish in bronze medal position as Germany's Fabian Hambuchen claimed silver.
'I still can't believe it,' Zonderland said. 'It's unique to be in an 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.
'I didn't expect to be so nervous. I had a good preperation and my training was good and I was ready for it.
'I was really happy that I came through my whole routine. It was a bit of a fight to get through the routine, but I did everything I could and this is the result.'