Maldonado was traveling east on W.Va. 45 and was wearing his seat belt, Boober said.
The crash occurred a short distance west of the intersection of W.Va. 45 and Files Crossroads, said Lt. Josh Smith of the Baker Heights Volunteer Fire Department.
Maldonado was traveling in a sport utility vehicle, Smith said.
Smith said he could not tell how the vehicle crashed. He said the vehicle was in the road when he arrived.
Rescue workers worked for about 21/2 hours to cut Maldonado from the wreckage, Smith said.
The Shepherdstown Fire Department and the Martinsburg Fire Department also assisted in the rescue efforts, Smith said.
Boober said it was unclear if the crash was weather-related.
The W.Va. 45 crash was the second fatal vehicle accident in two days in the Tri-State area.
Police said Paige Elizabeth Andrews, 24, of 1121 Lindsay Lane in Hagerstown, died after her car struck a guardrail in the eastbound lane of Interstate 70 in Frederick County, Md., early Saturday.
Andrews lost control of the 1990 Ford Taurus she was driving, went off the road east of the South Mountain rest area, hit the guardrail and continued east for about a half mile, police said.