But, Williams quickly reminded her guest that he was on her purple coach.
"Excuse me. This side of the couch is for the asking of the questions," a shocked Williams responded, before pointing over to him."That side is for giving up the information."
The CNN political contributor did diplomatically address Williams' queries about his relationship, calling Carter "my best friend 20 years ago and she's my best friend today."
Jones announced his pending divorce on Instagram in September, writing, "Divorce means the end of a marriage, not the end of a family. #FamilyForever." He shares two children with Carter.
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Williams continued to dig for dirt, asking the attorney if he will continue to wear his wedding ring while dating.
His reply? "You getting personal man. First of all, I got no dating life…I'm good. I'm just trying to save the world."
Watch the exchange, starting at 8:59.
Williams confirmed her divorce from husband Kevin Hunter on her talk show earlier this month during her "Hot Topics" segment.
"It's crazy because now my business is your business," she said, while laughing, "It's kind of funny. Turnabouts a fair game, I get it."
Her attorney, Mary Vidas, says divorce papers were filed in Essex County, New Jersey, where she has a home. Williams and television producer have been married since 1997 and share one child, Kevin Hunter Jr., 19.
Contributing: Sara M Moniuszko
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