Pope Francis has appealed to the governor of Oklahoma to commute an inmate's death sentence.
The Pope sent a similar plea this week to Georgia officials to spare the life of inmate Kelly Gissendaner.
However, Ms Gissendaner, who ordered her husband's murder, was executed by lethal injection on Wednesday after a number of legal appeals.
During the pontiff's visit last week to the US, the Pope urged Congress to abolish the death penalty.
The pope's representative Archbishop Carlo Maria Vigano wrote Oklahoma Governor Mary Fallin about the case of Richard Glossip on 19 September.
Glossip, convicted of conspiring to kill his boss, is set to die by lethal injection on Wednesday afternoon.
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He and his family have maintained his innocence for nearly 20 years, arguing that he was set up.
His co-worker Adam Sneed was convicted in 1997 of fatally beating their boss Barry Van Treese, the owner of the Oklahoma City motel where they both worked.
Sneed had been a key prosecution witness against Glossip but his attorneys had said they had an affidavit from another inmate who said Sneed admitted to setting Glossip up.
An Oklahoma court had agreed to halt his execution that had been scheduled for two weeks ago when his lawyers brought up that new evidence for review.
That court has not called to stop Wednesday's execution.
Ms Fallin said at the time she would respect whatever decision the appeals court made after lawyers reviewed new evidence.
Glossip also served as a plaintiff in a case that argued the sedative midazolam violated the US's ban on cruel and unusual punishment.
The US Supreme Court upheld Oklahoma's three-drug formula for lethal injections in June, allowing his execution to proceed.
The Pope has stepped up his advocacy against the death penalty in recent weeks.
"Every life is sacred, every human person is endowed with an inalienable dignity, and society can only benefit from the rehabilitation of those convicted of crimes," the Pope told Congress last week.
Several other high profile people including British billionaire Richard Branson and actress Susan Sarandon have also urged that Glossip not be executed.
Mr Branson took out a full-page ad in The Oklahoman newspaper on Wednesday that argued that Glossip is innocent.
The ad says there is a "breathtaking" lack of evidence in the case.
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