- He was a social worker, working especially with young people. He also was very involved with his community, arranging events, before becoming an actor.
- Born in Puerto Rico, but grew up in the East Village section of Manhattan, in New York City. In an interview, he explained that his mother traveled to New York fifteen minutes after his birth.
- He prefers his first name pronounced LOO-ee.
- In the show Community, he is portrayed as a former student of Greendale. Ironically he attended City College the rival school of Greendale.
- Was considered for the role of Willie Lopez in Ghost (1990). The role went to Rick Aviles instead. Their resemblance is so uncanny that people often ask Luis why he "killed" Patrick Swayze. He has to explain to them that it wasn't him, it was Rick.
- Performed in several spots for Cabot Cheese, which is based near where he lives in Cabot, Vermont, living the life of a gentleman farmer.
- Frequently cast by film director Steven Soderbergh.
- Frequently associated with crime movies, either playing thugs or cops.
- Frequently cast by film director Paul Thomas Anderson.
- He and Chuck Zito are the only actors to appear in both Carlito's Way (1993) and its prequel, Carlito's Way: Rise to Power (2005).
- Formerly of Cabot, VT, now resides elsewhere in the "Northeast Kingdom" area of the state. (2009)
- Friends with Debra Messing.
- Although he played the father of Nicholas Turturro on two episodes of NYPD Blue (1993), he is in fact only five years older than Turturro.
- Is the second Puerto Rican born actor to play Gomez Addams. The first being Raul Julia in The Addams Family (1991) and it's sequel The Addams Family Values (1993).
- Last name is pronounced gooz-MAHN.
- Has been in two movies with the word "way" in the title: The Cowboy Way (1994) and Carlito's Way (1993).
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