- His neighbor in Ketchum, Idaho, was Batman (1966) star Adam West. The two were good friends. In 1967, Williams and Bruce Lee guest-starred opposite West in the "Batman's Satisfaction" and two other episodes of Batman.
- Was the last surviving cast member of The Green Hornet (1966).
- Allegedly turned down a recurring role on Falcon Crest (1981) in the 1980s in order to focus on his business interests.
- During the run of The Green Hornet (1966), Williams pushed to give more screen time for co-star Bruce Lee, both to help his friend and martial-arts instructor and to help the show survive by playing up the most popular cast member of the show. The producers refused since they didn't want to take attention away from the star.
- Spent several months a year in Southern California as a reserve deputy with the Malibu station of the Los Angeles County Sheriff's Department.
- He and his long-time wife Vicki have three children. They met in Hawaii where she was a surfing pro. He also has twin daughters from a prior marriage.
- Van Williams passed away on November 28, 2016, at age 82, less than six and a half months before friend, neighbor, and 1960s co-star Adam West passed away on June 9, 2017, at age 88.
- Upon his death, he was cremated and his ashes returned to his wife.
- He was a lifelong conservative Republican.
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