The execution was carried out shortly after 6:30 p.m. CDT at the state penitentiary in Parchman.
It is one of two executions set in as many days. Gerald James Holland is scheduled to be executed Thursday at 6 p.m.
Woodward, 62, was convicted of capital murder in 1987 for raping and killing Rhonda Crane, a Jackson County Youth Court volunteer.
Crane was driving in July 1986 to join her parents for a family camping trip when Woodward used his log truck to force her to stop on Mississippi Highway 29 south of New Augusta, prosecutors said.
Woodward, who was 38 at the time, kidnapped and raped Crane, then shot her to death, prosecutors said.
Corrections Commissioner Christopher Epps said Woodward asked that his body be turned over to the University of Mississippi Medical Center in Jackson.
He said Woodward asked for no family members to witness the execution. Epps said Woodward appeared in a good mood as he prepared to die.
The Mississippi Supreme Court declined to halt the executions of Woodward and Holland.
Both filed clemency requests with Gov. Haley Barbour, who denied the clemency request for Woodward on Wednesday afternoon.
Holland,72, was sentenced to death for raping and killing 15-year-old Krystal King of Gulfport in 1987. He is the oldest death-row inmate in Mississippi.
The Mississippi Supreme Court on Wednesday refused to stop Holland's execution based on the appeal of a lawsuit filed on behalf of 16 condemned inmates.
Woodward was not a party in that lawsuit.
A lawyer for the 16 Mississippi death row inmates filed the appeal Tuesday after a lawsuit claiming the state provided inadequate legal counsel was dismissed in Hinds County Chancery Court.
The last back-to-back executions happened in 1961, according to Mississippi Department of Corrections records. Howard Cook was executed on Dec. 19, 1961, and Ellic Lee was put to death the following day. Both had been convicted of rape and died in the gas chamber, which was replaced by lethal injection in 1998.
The last execution in Mississippi was July 23, 2008, when Dale Leo Bishop was executed for his role in the 1998 slaying of 22-year-old Marcus Gentry of Fulton.