The 20-year-old trailed Zhou through the first five dives and was more than 30 points adrift prior to the final dive.
Zhou, perhaps feeling the weight of a nation's expectations, fluffed his final dive, a reverse three-and-a-half somersault.
World number three Mitcham nailed a sublime back two-and-a-half somersault with two-and-a-half twists, with a 3.8 degree of difficulty, achieving four perfect 10s.
He finished with 537.95 points to claim the gold and Zhou was left with a silver medal with 533.15 points.
"It's going to take a while to sink in," Mitcham said.
"My cheeks hurt from smiling, my face hurts from the chlorine, my legs are sore from jumping up and down.
"I'm in pain and I'm tired, but I'm so happy."
Zhou admitted he had started to become nervous in front of his home crowd.
"At the beginning I wasn't nervous, so I started well," Zhou said.
"The last dive was not as good as I could have done because I started to get nervous."
World champion Gleb Galperin of Russia snagged the bronze with 525.80 points as China's Huo Liang, first after the semi-finals, was shut out of the medals in fourth.
China, with seven titles already in the bag, was trying to become the first country since 1952 to win every diving gold on offer at a Games.
Australia's other competitor Mathew Helm finished in sixth, unable to add to his silver medal in the event in Athens four years ago.
Mitcham has become the first Australian man to win a diving gold medal since 1924.
Mitcham says he is completely surprised by his win.
"I'm going to watch the footage when I get home and I suppose I'll be impressed then because I don't even know how I dived, I don't even know what scores I got," he said.
"Because you just, you're not really in there. In the moment. You're just concentrating on your dive so much."
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