Labour leader Jacinda Ardern and her deputy Kelvin Davis will lead the party's negotiating team in coalition talks with NZ First.
Ms Ardern's announcement on Tuesday followed meetings with her senior MPs and party officials.
Additional members of the team are still to be decided, but Ms Ardern is anxious to get on with the job of forming a government with NZ First.
"We've indicated to NZ First that we're ready to go when they are," she told reporters.
NZ First leader Winston Peters is due to brief his caucus on Wednesday, which will be an important step in the process.
Ms Ardern has set her senior MPs the task of going through all the Labour, NZ First and Green Party policies to see how they line up, and where the differences are.
She'll be negotiating a three-way coalition government which includes the Greens.
Labour doesn't have enough seats to form a two-party coalition.
Mr Ardern expects her party and the Greens to initially negotiate separately with NZ First, with three-way talks further down the track.
The Greens have announced that party leader James Shaw will lead their team, which includes MP Eugenie Sage and three senior party officials.
National does have enough seats to form a two-party coalition, and that's what Prime Minister Bill English will be trying to do.
He has brushed off suggestions personality conflicts could affect National's negotiations with NZ First, and said on Tuesday discussions at staff level were continuing about organising the meetings.
Mr English didn't think any previous issues between himself and Mr Peters, or between National and NZ First, would have an impact on the outcome.
"It's a much bigger picture than discussion about personalities or particular issues between politicians," he told reporters.
"Mr Peters is an experienced politician, he takes his role very seriously, and I expect to begin negotiations on that basis."
Mr English said he expected negotiations would begin after Mr Peters had spoken to his caucus on Wednesday.
"There are ongoing discussions about the practicalities of organising a meeting in the next couple of days."
He said he hadn't formed his negotiating team and wouldn't do so until he had spoken to Mr Peters.
That didn't mean he was going to ask who should be on it.
"There's two parties to a negotiation, you work through what is going to work for everyone."