Nicola Sturgeon met Christine Lagarde in Washington as part of a four-day visit to America.
The SNP leader has made gender equality a key priority since becoming FM.
Ms Sturgeon also discussed the state of Scotland's economy during her talks with Ms Lagarde, a spokesman said.
Forbes magazine currently ranks Ms Lagarde as the sixth most powerful woman in the world.
She was first female chairman of elite law firm Baker & McKenzie and the first female finance minister in France and the wider G7, before her appointment to the top of the IMF in 2011.
A spokesman for Ms Sturgeon said: "The first minister had a productive discussion with Christine Lagarde on the current position of the Scottish economy and the Scottish government's approach to increasing competitiveness and tackling inequality.
"The first minister and Ms Lagarde also discussed the shared interest between Scotland and the IMF in increasing female participation in the economy and improving the representation of women at all levels in business."
During Ms Sturgeon's visit she has met US Deputy Secretary of State Tony Blinken, addressed an audience at the World Bank with a speech about economic equality and appeared on one of American television's top chat shows, The Daily Show, hosted by Jon Stewart.
On the first day, the first minister went to the Daniel Hale Williams elementary school in Brooklyn in the hope of learning lessons from the New York education system on improving attainment in Scottish schools.
Ms Sturgeon also hosted a reception in the United States to thank supporters of the fire-damaged Glasgow School of Art (GSA).
Scotland's first woman first minister has urged the female boss of the International Monetary Fund (IMF) to help increase the number of women at all levels of business.