Barnaby Joyce has previously denied the sexual harassment claim as 'spurious and defamatory'.
The woman who has accused Barnaby Joyce of sexual harassment says she wants him to be held to account for his alleged behaviour.
Mr Joyce, who has been on personal leave this week with new partner and former staffer Vikki Campion, will officially quit as Nationals leader on Monday and go to the backbench.
The deputy prime minister said the 2011 sexual harassment allegation, which is the subject of a Nationals investigation, was the "final straw" which led to his decision to quit.
A spokesman for Mr Joyce previously told News Corp he had been made "indirectly aware" of the claim which he described as "spurious and defamatory".
The woman has been named by The Weekend Australian as former West Australian Rural Woman of the Year Catherine Marriott.
She was the former Kimberley Pilbara Cattlemen's Association chief executive and is Co-operative Research Centre for Developing Northern Australia's Western Australia project manager.
In a statement released on Saturday, Ms Marriott said she never intended the issue to become public.
"I requested that a formal and confidential investigation into this incident be undertaken by the National Party to ensure there is accountability in relation to the incident I raise, and to prevent this type of inappropriate behaviour towards women in the future," the statement said.
"This complaint was not made solely to address the incident against me - it is about speaking up against inappropriate behaviour by all people in powerful positions."
Her lawyer, Emma Salerno, said Ms Marriott hoped her complaint would see the party develop clear processes for handling such complaints.
Ms Salerno said Ms Marriott never wanted to go public with the complaint and has not taken it to the police "at this stage".
Mr Joyce has asked the Nationals to refer the allegations to police.
Speaking to reporters in Washington DC early on Saturday, Prime Minister Malcolm Turnbull thanked Mr Joyce for his service as deputy prime minister.
"He has personal issues that he has to address and he feels that he cannot do that from the dispatch box," Mr Turnbull said.
"The issues that have been the subject of discussion over the past two weeks have not been issues between Nationals and Liberals.
"We have a 95-year-old political alliance, the longest in Australian history and it is absolutely enduring."
Veterans Affairs Minister Michael McCormack is frontrunner to replace Mr Joyce when a leadership ballot is held in Canberra on Monday morning.
Former infrastructure minister Darren Chester and NSW backbencher Mark Coulton have thrown their support behind Mr McCormack, while deputy leader Bridget McKenzie has refused to say who she will back.
Mr McCormack's only confirmed challenger is assistant families minister and fellow NSW MP David Gillespie.
Deputy Labor leader Tanya Plibersek called for the coalition agreement to be released, saying it was extraordinary the Nationals would decide the new deputy prime minister based on a secret deal.
"Frankly, most Australians have never heard of most of these people," Ms Plibersek told reporters in Sydney on Saturday.
The scandal surrounding Mr Joyce dominated headlines for more than two weeks, overshadowing Mr Turnbull's current trip to the United States.
"It's incredibly important that there be a circuit-breaker, not just for the parliament but more importantly a circuit-breaker for Vikki, for my unborn child, my daughters and for Nat (Mr Joyce's wife)," Mr Joyce told reporters in Armidale on Friday.
Mr Joyce faced repeated questions about jobs given to Ms Campion and his parliamentary expenses.
"Over the last half a month, there has been a litany of allegations. I don't believe any of them have been sustained," Mr Joyce said.