The death of convicted killer Ledell Lee was expected to be the first in a series of back-to-back executions planned before a lethal injection drug expires on April 30.
Lee, one of eight inmates scheduled to receive the injection, was put on death row for the 1993 death of his neighbour Debra Reese.
He beat her to death with a tyre tool that her husband had given her to use for her own protection.
Lee was arrested less than an hour after the killing after spending some of the $300 he had stolen from Reese.
He was pronounced dead at 11.56 pm. Thursday, four minutes before his death warrant was due to expire.
The Associated Press reported Lee had showed no signs of consciousness two minutes after the start of his execution. He made no final statement and showed no apparent signs of suffering.
The state had originally scheduled four double executions over an 11-day period in April but the first three executions were cancelled because of various court decisions.
The US Supreme Court had cleared the way for Lee's execution less than an hour before his death warrant was set to expire at midnight, rejecting a round of last-minute appeals filed by his lawyer.
Court officials overturned a ruling blocking the use of a lethal injection drug that a supplier says was obtained by misleading the company.
"Arkansas' decision to rush through the execution of Mr. Lee just because its supply of lethal drugs are expiring at the end of the month denied him the opportunity to conduct DNA testing that could have proven his innocence," said Nina Morrison, senior staff attorney with the Innocence Project, a non-profit legal organisation that helped represent Lee in his last appeals.
Justices on Thursday reversed an order by Pulaski County Circuit Judge Alice Gray that halted the use of vecuronium bromide, one of three drugs used in the state's lethal injection process, in any execution.
McKesson Corp. says the state obtained the drug under false pretences and that it wants nothing to do with executions.