Nicola Sturgeon would be willing to work with an all-woman "emergency cabinet" to stop a no-deal Brexit.
The Scottish first minister said she had responded to an approach from Green MP Caroline Lucas to put together a group of female politicians to bring a "different perspective".
The SNP leader was appearing on Monday's edition of ITV's Loose Women.
She was the first guest in a series featuring what the programme called "trailblazing women".
Ms Sturgeon said of her invitation to join the proposed female cross-party cabinet: "I am happy to work with anybody, male or female, to stop Brexit."
Earlier on Monday, Caroline Lucas asked 10 female politicians from all parties to join her in forming an "emergency cabinet" in a bid to stop a no-deal Brexit.
As well as Nicola Sturgeon, Ms Lucas approached Labour's shadow foreign secretary Emily Thornberry, Liberal Democrat leader Jo Swinson and Conservative MP Justine Greening.
The others are Heidi Allen, Kirsty Blackman, Yvette Cooper, Sylvia Hermon, Liz Saville Roberts and Anna Soubry.
International Trade Secretary Liz Truss criticised the plan as sexist.
But 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" - the first arrangement of its kind since World War Two.
'Difficult and frustrating'
However, speaking about female politicians, Ms Sturgeon added: "Theresa May was a woman and she didn't manage to sort out Brexit."
She revealed that she found dealing with the former prime minister difficult.
She added: "Theresa May was very, very scripted, so when you were talking to her in private it was the same approach.
"It would be very difficult and frustrating to get into a discussion and to find some common ground."
Ms Sturgeon said she believed there were good and bad politicians but that women could be more empathetic and bring a different approach to politics.
She joined the Loose Women panel - Andrea Mclean, Brenda Edwards, Carol McGiffin and Gloria Hunniford - to discuss topics including entering the world of politics, what she does to de-stress and her miscarriage in 2011.
When asked if she felt unfairly judged for not having children, she said: "I was constantly asked about it. It's okay for a while in your 20s and 30s but it becomes intrusive."
She said that the reason she went public about her personal loss five years later was to remove the taboo about talking about it and to try to stop the questions about children.
'That guy that talks nonsense'
The first minister said she supported the idea of miscarriage leave proposed by New Zealand Prime Minister Jacinda Ardern, and she agreed society should adapt to speaking about it to create a greater understanding.
She continued: "There was this assumption that I took a hard-nosed decision to prioritise a career over children.
"Women should not be judged for the reasons they have or don't have children."
Ms Sturgeon concluded her interview with a tongue-in-cheek swipe at the new Prime Minister Boris Johnson.
She joked: "Boris and I... are not very alike.
"He is, you know, that kind of guy that talks nonsense but has that swagger, confidence and conviction."