Floyd DeVos of Grand Rapids was pronounced dead at the scene Wednesday night on the Seven Mile Bridge.
His wife, Nancy, was hospitalized Thursday night in critical condition.
The Florida Highway Patrol reported that the car DeVos was driving south over the bridge was struck by a car that Xavier Ycaza of Golden Beach was driving north. Ycaza's car struck the wall and caught fire.
Police said two Monroe County deputies pulled Ycaza to safety before he was badly burned. Ycaza was hospitalized in stable condition.
Toxicology tests are pending.
The crash closed the bridge in both directions for three hours.