Spencer will assume her duties at the organization on April 3, following a national search and transition period, board chairman Jeff Wahlen said.
She replaces Wendy Walker, who served in the position for more than 27 years and will become president emeritus.
“Having dedicated my professional career to engaging citizens to do what is best for their community, this position is a dream come true,” Spencer said. “ I look forward to hitting the ground running next spring.”
Spencer is chief executive officer of the Corp. for National and Community Service, a $1.1 billion federal agency that runs AmeriCorps, the Senior Corps and the Social Innovation Fund.
It works with state commissions including Volunteer Florida, which Spencer ran between 2003 and 2012, following her appointment by former Gov. Jeb Bush.
Earlier, she ran the Florida Park Service and was campaign director for United Way of the Big Bend.