State police say William Martin suffered a "medical episode" early Tuesday while transporting a burn victim from the deadly blaze in Stillwater, about 35 miles west of New York City.
Seventy-year-old Dorothy Baer was pronounced dead at the scene of the fire. Martin was taking her husband, John, to a helicopter to be transported to a hospital when he struck a utility pole and the ambulance partially overturned.
John Baer's condition wasn't immediately available but police say he wasn't injured in the crash. Martin was pronounced dead at a hospital.
Investigators say John Baer told them he found his wife on fire in their living room. The fire's cause is under investigation.