Julie Bentley, who has been at Girlguiding since 2012, will take up post on 1 August, succeeding Sir Tony Hawkhead, who stepped down in February.
Bentley said: "I will be very sad to leave Girlguiding, which is a fantastic charity working with hundreds of thousands of girls and young women every year.
"But after almost six years it felt time to hand over the baton and take on a new challenge myself.
"Action for Children works with some of the most disadvantaged children and young people in our society, their work is crucial and it will be an honour to join the trustees and staff and volunteers to take the charity forward."
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