The 61-year-old, who has spent nearly all of his adult life on death row, is scheduled to die Thursday night.
States have moved away from the electric chair in recent decades - and no state uses electrocution as its main execution method anymore.
Tennessee plans to execute by electric chair on Thursday a 61-year-old man who has spent more than 36 years on the state's death row.
Both inmates had argued in court that Tennessee's current method, involving the drug midazolam, involves a prolonged and torturous death. Miller was placed on death watch Tuesday despite his legal team's work to delay the execution.
Lethal injection is the preferred method of putting people to death in all USA states that have the death penalty, according to the Death Penalty Information Center.
Convicted murderer Edmund Zagorski, who was executed on 1 November, had also chosen the electric chair over lethal injection, despite proponents saying this method is painless and humane. His attorney has filed for a stay to the execution with the U.S. Supreme Court.
Miller won some time after capital punishment in Tennessee was suspended because of controversy over the chemicals used in lethal injections.
In Tennessee, inmates whose crimes were committed before 1999 can chose electrocution over lethal injection.
He was convicted of killing a 23-year-old mentally handicapped woman in 1981 in Knoxville.
Gov. Bill Haslam ordered a brief reprieve to "give all involved the time necessary to carry out the sentence in an orderly and careful manner".
Some inmates have argued death by electric chair rather than lethal injection is "the lesser of two evils".
Zagorski's execution was delayed for about three weeks after he requested the electric chair amid a last-minute flurry of legal manoeuvres. He was the second inmate in more than a month to choose electrocution.
With only hours left before his scheduled execution in the electric chair, a Tennessee inmate is waiting for a response from the U.S. Supreme Court on two applications to halt the procedure.
Haslam has already rejected similar requests from other death row inmates this year.