The 40-year-old Keeping Up With The Kardashians star and criminal justice reform campaigner launched a last-ditch attempt to save Brandon Bernard, a 40-year-old imprisoned in Indiana.
Bernard was sentenced to death in 2000 after being found guilty of two counts of murder.
At the age of 18 he was involved in the abduction and robbery of two youth ministers in Texas.
Kim has described the crime as "terrible" but argued Bernard's role was "minor compared to that of the other teens involved, two of whom are home from prison now".
She has now looked to use her influence in persuading President Trump to intervene and stop the execution.
The reality star tweeted: "Most of the time executions happen, in our names, without a lot of attention given to them. This is unacceptable.
"For the next 24 hours I will be tweeting about Brandon and his case and why his life should be spared by @realDonaldTrump."
The mother-of-four urged her followers to tweet the president asking him to act.
Campaigners have been working to save Bernard's life, arguing that during his trial prosecutors withheld evidence that could have influenced the jury at sentencing.
They say he only occupied the "lowest rung" of the gang with whom prosecutors alleged he and his co-defendants were affiliated.
Bernard was sentenced to death for his part in the murders of Todd and Stacie Bagley. Some of his accomplices were under 18 and ineligible for the federal death penalty so received jail sentences.
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