He becomes the second-biggest lottery winner ever in Australia, being the only division one winning entry in the draw.
The only Australian lottery player to have won more than the man was a Sydney nurse who scored more than $107m in January 2019.
The man initially told lottery officials he would continue working - but his wife had other ideas.
"I will continue to work. But I need to process this a bit more. Maybe I won't in the future!" the man said.
"Working?! We're multi-millionaires now!" his wife interjected.
The man erupted into hysterical laughter and slapped his face to ensure he wasn't dreaming, when he received the life-changing call.
"Are you sure?! Have you got the right person?" he said.
"I'm with my wife right now. She's in shock.
"We're going to struggle to sleep tonight."
The man said the couple will buy a new house and set themselves up for the future.
"This is unbelievable! I've won $100 million!? Am I dreaming? I'm a millionaire now?!" he said.
As well as the sole division one winner, there were a total of 3,867,940 prizes worth more than $77.61 million won in Thursday's Powerball, including 10 division two winners, who each took home $216,070.
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