Batman Returns (1992)
Certainly not my favorite Batman film and with even more certainty not my favorite Batman villain, but DeVito as the Penguin just seemed to work in my opinion. Strangely, I liked Burgess Meredith in the TV show in the role better but for the movie and the vision that Burton had for his film franchise, DeVito did a great job in the role.
Also starring in this 2nd installment of the Burton/Schumacher franchise was Michael Keaton in his last appearance as Bruce Wayne/Batman, Michelle Pfeiffer as Selina Kyle/Catwoman, and Christopher Walken as businessman Max Shreck. Paul Reubens did a cameo as the father of The Penguin (aka Oswald Cobblepot).
DeVito even got a nomination for Best Movie Villain at the MTV Movie Awards. He lost to Jennifer Jason Leigh in Single White Female.
Another one of my favorite biopics, this one is about the famous missing person, the Teamster boss Jimmy Hoffa, who was played brilliantly by Jack Nicholson.
DeVito actually directed this film and the character that he played, Bobby Ciaro, is actually a fictional character based on several people in Hoffa's life.
Also starring in this film are J.T. Walsh as Frank Fitzsimmons, the man that took over the Teamsters when Hoffa went to jail, Armand Assante, and John C. Reilly.
Renaissance Man (1994)
In this film directed by Penny Marshall (Big, A League of Their Own, TVs Laverne from Laverne and Shirley), DeVito plays Bill Rago, an unemployed advertising executive that finds himself teaching English to a group of U.S. Army recruits.
It also stars Gregory Hines as the group's drill sergeant and Mark Wahlberg as Pvt. Tommy Lee Haywood.
Romancing the Stone (1984)