Lucy de Groot, chief executive of Community Service Volunteers, will retire in October.
De Groot, who has led CSV since February 2011, will be succeeded by Oonagh Aitken, the charity’s director of social action and volunteering.
De Groot said that the charity was in a more stable place than when she joined and it was a good time for her to "pass the baton".
She has led the charity through a major restructure after it lost £1.1m in strategic partner funding from the Cabinet Office in April 2011, which led to the closure of all 12 of its learning centres, affecting 110 jobs.
"It has been a very intensive three and a half years," she told Third Sector. "I am delighted that I am now able to retire as CSV’s chief executive confident that we have in place the foundations of a strong, modern charity."
Aitken said the charity had come a long way in the past three and half years "which is a testament to Lucy’s vision to modernise CSV and make the charity more focused, efficient and, most importantly, relevant for the future. Difficult decisions have had to be made, including the closure of our learning operations.
"But the continued hard work of staff and volunteers has cemented our position as the go-to volunteering and social action charity, and we are now entering a new period of growth and expansion on a secure financial basis."
De Groot took over from Dame Elisabeth Hoodless, who stood down in 2011 after 47 years at the charity.