The Trump administration has carried out its 13th federal execution since July - the most of any presidency in more than 100 years.
Dustin Higgs was convicted of murdering three women in a Maryland wildlife refuge in 1996.
The 48-year-old was the third inmate to receive a lethal injection at the federal prison in Terre Haute, Indiana, this week.
He was pronounced dead at 1.23am local time (6.23am UK time) on Saturday.
The justice department resumed federal executions last year following a 17-year hiatus.
No president in more than 120 years has overseen as many federal executions.
Not since the waning days of Grover Cleveland's presidency in the late 1800s has the US government executed federal inmates during a presidential transition, according to the Death Penalty Information Centre.
Mr Cleveland's presidency was also the last time in which the number of civilians executed federally was in double digits in one year, during his second term in 1896.
The number of federal death sentences carried out under Mr Trump since 2020 is more than in the previous 56 years combined, reducing the number of prisoners on federal death row by nearly a quarter.
It is likely none of the around 50 remaining men will be executed anytime soon, with Mr Biden signalling his intention to end federal executions.
Lisa Montgomery, the only woman on death row, was executed on Wednesday for killing a pregnant woman.
She had cut the baby out of the woman's womb and claimed it as her own.
Montgomery was the first woman executed in nearly 70 years.
Federal executions began as the coronavirus pandemic raged through prisons nationwide.
Higgs and former drug trafficker Corey Johnson, who was executed on Thursday, were among those to have contracted coronavirus last month.
Some members of the execution teams have also previously tested positive for the virus.
Higgs was convicted of first-degree murder and kidnapping in the killings of Tamika Black, 19; Mishann Chinn, 23; and Tanji Jackson, 21.
He was found guilty by a federal jury in Maryland in October 2000.
His death sentence was the first imposed in the modern era of the federal system in Maryland, which abolished the death penalty in 2013.
Higgs' lawyers argued it was "arbitrary and inequitable" to execute Higgs while Willis Haynes, the man who fired the shots that killed the women, was spared a death sentence.
The federal judge who presided over Higgs' trial two decades ago said he "merits little compassion".
US district judge Peter Messitte wrote in a 29 December ruling: "He received a fair trial and was convicted and sentenced to death by a unanimous jury for a despicable crime."
Shawn Nolan, Higgs' attorney, said in a statement after the execution that his client had spent decades on death row helping other inmates and "working tirelessly to fight his unjust convictions".
Mr Nolan said: "The government completed its unprecedented slaughter of 13 human beings tonight by killing Dustin Higgs, a black man who never killed anyone, on Martin Luther King's birthday.
"There was no reason to kill him, particularly during the pandemic and when he, himself, was sick with COVID that he contracted because of these irresponsible, super-spreader executions."
Higgs' 19 December petition for clemency argued he had been a model prisoner and dedicated father to a son born shortly after his arrest.
He had a traumatic childhood and lost his mother to cancer when he was 10, the petition said.
His attorneys wrote: "Mr. Higgs's difficult upbringing was not meaningfully presented to the jury at trial."