The 85-year-old former CNN host filed for divorce from Shawn King, 59, in Los Angeles Superior Court on Tuesday, according to paperwork obtained by CNN.
The pair married on September 5, 1997, and their date of separation is listed as June 6, 2019, in the filing.
The request for divorce cites irreconcilable differences as the reason for the split.
This union marks King's eighth marriage to seven women. He was wed to former wife Alene Akins twice.
He and Shawn King have two sons, Chance, 20, and Cannon, 19.
It's the second time Larry King has sought to end the marriage.
He filed for divorce from the former singer and TV presenter back in 2010 but withdrew his petition after the pair reconciled.
Over the weekend he tweeted a photo with his sons. "I'm so proud of my boys...," King wrote in the tweet.
CNN has reached out to reps for the couple for comment. As of early Wednesday, neither had commented on social media about the filing.