Former NSW trade commissioner Mike Newman, 54, will stand as the party's lead candidate and run in the traditionally Labor voting seat of Cessnock in the Hunter Valley.
He said he would campaign on regional issues and business in a statement released on Friday.
"We'll be focusing on issues which matter in NSW like the cost of living, our housing crisis and the neglect of our regional communities and rural industries under Labor," he said.
"We will prioritise policy settings which create a much better environment for businesses so they can focus on what they do best: create jobs, grow the economy and increase prosperity in our state. We need to make NSW competitive again."
Senator Hanson also affirmed serial One Nation candidate and coal miner Stuart Bonds would lead her upper house ticket.
The 40-year-old cattle farmer also hails from the Hunter and announced he would campaign on issues affecting primary industries.
"One Nation backs our miners and our farmers. We back our regional communities. We'll be campaigning hard on policies support these industries and the communities which rely on them," he said.
Ms Hanson said, together, the men "will be a formidable team to lead our party at the NSW election".
The state election is slated for March 13, 2027.
The Labor government wasted no time levelling their first barb at the pair on Friday morning.
Labor's Maitland MP Jenny Aitchison said the hopefuls joined a party with a poor track record in the Hunter.
"One Nation's new leader wants to represent the Hunter, but Mr Newman and his own party don't seem to believe there's a future for train manufacturing in the Hunter," she said.
She called on Mr Newman to explain if he supported One Nation's position on whether trains should be built in the Hunter Region instead of overseas.
Mr Newman's running mate, Mr Bonds, had publicly criticised her government's multi-billion-dollar investment to return train manufacturing to the state, she said.
"They talk a big game about Australian jobs, but when we make the decision to bring those jobs home, their answer is to send the work overseas … Backing Australian workers means actually giving Australian workers the work, it can't just be a slogan," she said.
Former deputy premier John Barilaro appointed Mr Newman NSW's senior investment commissioner to Japan and Korea in 2021.
He left the role shortly before the Minns government axed the position, and has spent decades working around the world in financial services.