Rhee, who served as Washington D.C. schools chancellor for three years, said in a statement that she will be focusing on her family and supporting her husband, Sacramento Mayor
"His focus and passion for underserved communities and ensuring access to equal opportunity will be central to whatever comes next for us," Rhee said.
The move was first reported by the Huffington Post. A StudentsFirst spokesperson confirmed that Rhee will down as CEO, but did not specify when she will do so.
Her time leading D.C. schools vaulted her into national prominence, as she battled teacher unions, closed underperforming schools and fired hundreds of teachers rated as ineffective by an evaluation system based largely on student test scores.
Rhee then founded StudentsFirst, which has focused heavily on national lobbying, policy and campaign work. The group served to counter teachers unions and to continue pursuing Rhee's goals: pushing for policies that limit teacher tenure, softening rules for dismissing teachers and including test scores as a major factor in evaluating instructors.
Rhee said she created the group to champion and advocate for students.
"I'm so proud of what we've accomplished at StudentsFirst and look forward to being actively involved as we become an even more effective advocate for kids," she said. "We've been successful in challenging the status quo, and that's something I will never stop doing."