Chief Kimberly Jonathan will lead the group until a new chief is elected at an assembly in October 2015.
Jonathan took over after former FSIN Chief Perry Bellegarde was voted national chief of the Assembly of First Nations on Wednesday.
Jonathan, who is Dakota and Cree, was elected as the first vice-chief in 2012.
Previously, she worked with the Prince Albert Grand Council and at the White Buffalo Treatment Centre for youth.
Throughout her career, she was a board member with the First Nations University of Canada and with Indian Child and Family Services.
"As the first female chief of the federation, it's so exciting," Jonathan said Thursday after returning from the assembly's meeting in Winnipeg.
"I think of the people right in their homes, at our home communities, our home fires, within our nations and what message this is sending our baby girls that are there.
"Any time we have an indigenous woman take the reins of anything and accomplish so much, it's not their individual accomplishment ... it's our nation's accomplishments."
Jonathan pointed to the work of First Nations women across the province, including Okanese First Nation Chief Marie-Anne Daywalker-Pelletier and her vice-chief, Heather Bear.
She said indigenous women are standing up and being heard on their own terms.
"What makes it OK for our women to be disrespected? What makes it OK for our women to be hurt and violated on many fronts?
"It's time to push through that and plow through that and take our rightful place as indigenous women and as leaders. To let people know that it's not OK, it never was OK, and we will not tolerate that."
She said her experience as a mother, an advocate and a member of the FSIN have shaped her priorities, which include child welfare, non-insured health benefits, missing and murdered indigenous women, and understanding underlying issues linked to poverty and violence.
"What I bring to the table are those strengths of the teachings and values of ceremony," she said.
Jonathan said it's good to know a Saskatchewan friend and colleague will be at the helm of the AFN.
"There will be a huge strength for Saskatchewan nations because (Bellegarde) understands the needs for Saskatchewan nations and he understands the direction of the chiefs."
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