It is the second time Trump has asked the justices to quash damages awarded by a jury to Carroll, a longtime advice columnist and former TV talk show host.
The Supreme Court refused in June to hear his appeal of another verdict, for $US5 million ($A7.2 million), that found him liable for sexual abuse and defamation.
The latest case centres on comments Trump made during his first term as president. The Justice Department wants to invoke the Westfall Act, which shields government employees from being sued for doing their jobs.
"Absent this court's intervention, the sitting president is facing nearly a hundred million dollars of personal liability for conduct that was well within the scope of his federal office," federal attorneys wrote.
"That alone deserves this court's attention."
The documents were reviewed on Wednesday by The Associated Press and expected to be formally docketed with the court shortly.
Trump's lawyers, meanwhile, argued that an appeals court "engaged in procedural contortions" to avoid addressing Trump's claims that presidential immunity protects him from the $US83 million ($A119 million) award because he made the statements in question in 2019 while he was president.
The lawyers argued that the 2nd US Circuit Court of Appeals in Manhattan ruled in a manner that "cries out for this court's review in this unprecedented case" and called the damages "grossly excessive".
"This is the first case in our nation's history in which a court has imposed damages liability on a president for his conduct in office," the lawyers wrote.
Carroll's lawyers have declined to comment on the latest Trump filing.
Trump has long argued he cannot be sued over comments he made about Carroll during his first term where he disavowed knowing her and attacked her motivations for going public with her story in a recent memoir.
He is also asking the Supreme Court justices to reconsider their rejection of his appeal in the $US5 million ($A7.2 million) verdict.
The appeal comes about two years after the Supreme Court granted Trump broad immunity from criminal prosecution as a former president.
Carroll testified twice before New York juries that Trump sexually assaulted her in spring 1996 in a dressing room at Bergdorf Goodman, a luxury retailer across the street from Trump Tower. She first went public with the claims in a 2019 memoir.
She sued Trump for defamation after he accused her of making up the allegation to help book sales, adding that he'd never met her and "she's not my type."
He has repeatedly denied any wrongdoing.
A Manhattan jury awarded her $US83 million ($A119 million) in damages in January 2024.
Lower courts have so far rejected Trump's appeals to overturn the verdict, though the New York-based appeals court split over the decision and agreed to delay that payout until the Supreme Court weighs in.
In 2023, another jury said Carroll was entitled to $US5 million ($A7.2 million) after concluding that Trump had subjected her to sexual abuse in the department store encounter and for defamation for remarks he had made after his first term ended. That judgment has been paid.
The Associated Press does not identify people who say they have been sexually assaulted unless they come forward publicly, as Carroll has done.
