- He replaced Roy Thinnes in Alfred Hitchcock's Family Plot (1976) one month into the filming, after the legendary director found out that he was then available because Devane was Hitchcock's first choice for the part. Some long shots in the film are still of Thinnes, but all other footage was re-shot with Devane.
- Admits that he only did Poor White Trash (2000) for the money.
- When "One Flew Over the Cuckoo's Nest" debuted off-Broadway at the Mercer Arts Center as a stage play in 1971, he originated the role of Randall P. McMurphy.
- Best-known for political roles, largely because of his Kennedyesque looks and mannerisms. Played the President of the United States in Stargate SG-1 (1997), Stargate: Continuum (2008), The Dark Knight Rises (2012) and 24 (2001). Also played the Secretary of State in The West Wing (1999). Similarly, his character Greg Sumner on Knots Landing started as a politician.
- Owned a restaurant, Devane's, that specializes in New York-Italian cuisine. Originally located in Indio, the restaurant expanded to Rancho Mirage, CA. Additional restaurants in La Quinta and Palm Springs were slated for a 2008 opening, but due to the economy, they closed.
- Enjoys horseback riding. Is an avid polo player and has won many awards for it. Is a fly-fisher.
- Has the rare distinction of being in two movies that opened on the same weekend in the U.S.: Hollow Man (2000) and Space Cowboys (2000) (August 6, 2000).
- In Family Plot (1976) he plays the (adopted) son of a chauffeur and in real life he is an actual son of a chauffeur.
- Alumnus of the AADA (American Academy of Dramatic Arts), Class of 1961.
- Appeared with Donald Sutherland in Space Cowboys (2000). He later costarred with Donald's son, Kiefer Sutherland, in 24 (2001).
- Born on exactly the same date as George Lazenby (of "On Her Majesty's Secret Service" fame).
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