Berry is currently chief executive of the General Social Care Council, a position she has held since 2001. She will take over as head of the care charity for older people this September.
She was previously chief executive of the Equal Opportunities Commission for two years, before which she was executive director at the Charity Commission.
"Lynne has the experience, skills and confidence that we need," said Ruth Markland, chairman of WRVS. "Her decision to join is a vote of confidence in our plans to do more to improve the quality of life for older people."