Caroline Lucas has asked 10 female politicians from all parties to join her in forming an "emergency cabinet" in a bid to stop a no-deal Brexit.
Writing in the Guardian, the Green Party MP said the all-women cabinet could "bring a different perspective".
Ms Lucas, whose party wants another Brexit referendum, said the aim would be to force a no-confidence vote in Prime Minister Boris Johnson.
She would then hope to form a "national unity government".
This arrangement - when a group of MPs of multiple parties choose to work together and form a government - has not been seen since the Second World War.
Women 'less tribal'
In her Guardian article, Ms Lucas - a former Green Party leader - said the national unity government would "press the pause button" and organise another referendum offering a choice between staying in the EU or the government's Brexit plan, whether that is an agreed deal or no deal.
"In my experience, women tend to be less tribal, they tend to find it easier to establish trust more quickly," she told BBC Radio 4's Today programme.
She also added that her proposed unity government would have to be led by a female Labour MP, as they would be representing the largest opposition party.
But her idea was criticised by International Trade Secretary Liz Truss, who tweeted: "Is there anything more sexist than claiming your gender determines your worldview/behaviour/attitude?"
Among the women Ms Lucas has invited to join her are Labour's shadow foreign secretary Emily Thornberry, Liberal Democrat leader Jo Swinson, Scotland's First Minister Nicola Sturgeon, Conservative MP Justine Greening, and Plaid Cymru Westminster leader Liz Saville Roberts.
The others are: Heidi Allen, Kirsty Blackman, Yvette Cooper, Sylvia Hermon, and Anna Soubry. She has asked to meet the 10 women in the coming days.
On Monday, Ms Lucas told the BBC she had received responses from five of the women she has written to, expressing differing levels of interest.
She added she wasn't completely against involving men - for instance accepting that a key anti-Brexit campaigner like Dominic Grieve could be given a cabinet seat.
'Anger and resentment'
Ms Thornberry tweeted a reply to say she would not be able to take part in the planned talks because she is currently on holiday.
She added that returning the issue of Brexit "to the people" was the "best route to go down at this point".
"My fear with the other suggested route - imposing some alternative coalition government without any reference to the public - would risk worsening the feelings of anger and resentment towards 'Westminster' that have led us into this Brexit mess," she added.
Ms Saville Roberts welcomed Ms Lucas's bid to break the deadlock over Brexit, but said she was "not entirely comfortable" that only women would be involved.
Ms Lucas's suggestion has also attracted widespread discussion on social media, with many people expressing criticism.
Labour's shadow home secretary Diane Abbott tweeted it "won't work... whatever the gender of the participants".
Backdoor route to a National Government. Didn’t work for Ramsey Mcdonald and won’t work now, whatever the gender of the participants https://t.co/ru0CbHwrK4— Diane Abbott (@HackneyAbbott) August 11, 2019
Labour MP Clive Lewis called it a "very interesting proposal", but asked: "Where are the BAME women politicians?"
Ms Lucas replied to him, saying she agreed that the list should be opened out further and she would love Ms Abbott to be involved.