She will be London-based and will take charge of Anglo American’s relationships with governments in southern Africa, South America and Australia.
Hunter, who is married to Sky political editor Adam Boulton, will take up the position on 1 June.
The move comes 18 months after she left BP, where she was comms director. Under Blair, Hunter was director of government relations at Number 10 until 2001.
She replaces Edward Bickham.who is currently considering his next move. Bickam told PRWeek he was in talks with one major PR agency and one well-known company about a senior comms role.
He said he was leaving Anglo American after nine years because 'you need to revive and refresh.'
Bickham joined Anglo American in 2000 as group head of external affairs. He was previously deputy chairman and MD, corporate and public affairs at Hill & Knowlton. Prior to this he worked as a special adviser to various Conservative cabinet ministers.