Police said the incident happened at Miller Range, at Waitati, during a shooting club meet on Sunday afternoon.
Senior Constable Phil Beckwith, of Port Chalmers, said other members of the club drove the man to Dunedin Hospital.
The man was an experienced shooter and the gun, an older side-by-side double barrel shotgun, was his own.
It was possible self-made ammunition was being used at the time, but it was not yet known how or why the gun exploded.
Police were investigating the incident, but the Department of Labour might be notified at a later date, he said.