- Provided the growls for TV's El hombre increíble (1977).
- Served with the 11th Airborne.
- Was in two Star Trek series as diametrically-opposed characters: the Viaje a las estrellas (1966) episode, The Way to Eden (1969), as the paradise-seeking hippie Adam, and in the Star Trek: Deep Space Nine (1993) episode, Little Green Men (1995), as the no-nonsense General Denning at Area 51 who interrogates the Ferengis Quark, Rom, and Nog.
- Was friends with Hunter S. Thompson and Bill Bixby.
- Roger Ebert often referred to him as "that character actor with a smile like Jaws".
- Appeared in 10 films directed by Jonathan Demme.
- Enjoyed painting with watercolors.
- He was once asked in real life for "McElroy's" autograph, the front man for the Good Ol' Boys country-western band in the comedy The Blues Brothers (1980)... and gave it.
- Appeared in four Russ Meyer movies: Cherry, Harry & Raquel! (1969) (in which he went full frontal), Más allá del valle de las muñecas (1970) and The Seven Minutes (1971) (both of which he kept his clothes on), and Supervixens (1975) (in which he used a humongous rubber phallus or dildo as a "stand-in").
- Appeared on Doctor Phil (2002) with his wife to discuss his obsession with being famous.
- Played in two Kentucky high school state basketball championships.
- On Hombres de Negro: La serie animada (1997), Napier provided the voice of Zed, a role originally played in the live-action films by Rip Torn, who co-starred with Napier in the 1989 low-budget action flick, Hit List (1989).
- Worked as an on-the-road correspondent for the trucker magazine "Overdrive" in the early 1970s.
- Napier played a prison warden on at least three separate, unrelated occasions: Ernesto pierde su puesto (1990); in a 1999 episode of Walker, Texas Ranger (1993) (Fight or Die (1999)); and in several episodes of Los Simpson (1989).
- The second of three children born to a tobacco farmer (Linus Pitts Napier; died 1991, aged 102), and a homemaker. Charles Napier was stationed in Germany for three years while in the Army, serving with the 11th Airborne. He later earned a bachelor's degree in art from Western Kentucky University in 1961 and worked as a substitute teacher after arriving in Los Angeles in the mid-1960s.
- He has appeared in two films that have been selected for the National Film Registry by the Library of Congress as being "culturally, historically or aesthetically" significant: Los hermanos caradura (1980) and El silencio de los inocentes (1991).
- He made guest appearances on both Luisa y Clark: Las nuevas aventuras de Superman (1993) and Superman: La serie animada (1996).
- Napier starred in one of the first widely shown films to contain full frontal male nudity: Cherry, Harry & Raquel! (1969). It was such an event that "Variety", the Bible of Hollywood trade papers, contacted Napier's mother to find out her reaction to her son appearing in what was known in the exploitation industry as a "pickle shot.".
- He is survived by three offspring: son Charles Lewis "Chuck" Napier, Junior (B. June 23, 1964); son Hunter Charles Napier (B. May 10, 1988); and daughter Meghan Sara Lena Napier (B. June 11, 1991).
- He played a US Army officer who was involved in the Roswell UFO Incident in both Little Green Men (1995) and Summer of '47 (2000).
- His role in Walter Hill's Hard Times (1975) was cut from the final print.
- Was considered for the role of Sheriff Ed Landis in El infierno de Jason (1993).
- Having a cameo in Austin Powers: El espía seductor (1999), there's a joke about Dr. Evil getting away in a rocket that looks like a woman's husband's one-eyed monster. Coincidentally, 10 years later, he starred in a movie titled One-Eyed Monster (2008).
- He is interred at the Bakersfield National Cemetery in Bakersfield, California.
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