Relate chief executive Angela Sibson is the first chief executive of the Commission for the Compact.
Based in Birmingham, Sibson will work alongside John Stoker, who took up the post of Compact Commissioner in September.
She will run the organisation full time while Stoker works two days a week on the commission's strategy and meets ministers, civil servants and voluntary organisations.
"I believe a secure future for voluntary and community organisations rests on effective partnerships with the public sector," said Sibson. "Achieving that will be based on a principled, flexible, transparent approach."
Navca urged the commission to prioritise establishing local Compacts where they don't yet exist and to take "robust action" against local authorities that don't take the agreements seriously.
Kevin Curley, chief executive of Navca, said: "A stick and a carrot are needed. There are still 41 local authority areas in England without a Compact."