Yes. The first actress to win both awards was Helen Hayes, who won the 1970
Best Supporting Actress award for "Airport" 39 years after she won the 1931/32 Best Actress award for "The Sin of Madelon Claudet."
Since then, other actresses who have performed the double-category feat are:
The Academy Award for Best Supporting Actress of 1989 went to Ireland's Brenda Fricker for her performance in "My Left Foot."
She won Best Supporting Actress for The Accidental Tourist (1988).
No, Moonstruck is not the only movie to win both Best Actress and Best Supporting Actress. That feat has been accomplished seven (7) times. The following films also won both the Best Actress and Best Supporting Actress categories.Gone with the Wind 1939Actress (Vivien Leigh-won);Supporting Actress (Hattie McDaniel-won)Mrs. Miniver 1942Actress (Greer Garson-won);Supporting Actress (Teresa Wright-won)A Streetcar Named Desire 1951Actress (Vivien Leigh-won);Supporting Actress (Kim Hunter-won)Who's Afraid of Virginia Woolf? 1966Actress (Elizabeth Taylor-won);Supporting Actress (Sandy Dennis-won)Network 1976Actress (Faye Dunaway-won);Supporting Actress (Beatrice Straight-won)Moonstruck 1987Actress (Cher-won);Supporting Actress (Olympia Dukakis-won)Shakespeare in Love 1998Actress (Gwyneth Paltrow-won);Supporting Actress (Judi Dench-won)
The winner of the 2007 Oscar for Best Supporting Actress was Jennifer Hudson for Dreamgirls (2006).
Angelina Jolie won the Oscar for Best Actress in a Supporting Role in 1999.
Anjelica Huston won the Oscar for Best Actress in a Supporting Role in 1985.
Anne Revere won the Oscar for Best Actress in a Supporting Role in 1945.
Beatrice Straight won the Oscar for Best Actress in a Supporting Role in 1976.
Cate Blanchett won the Oscar for Best Actress in a Supporting Role in 2004.
Celeste Holm won the Oscar for Best Actress in a Supporting Role in 1947.
Claire Trevor won the Oscar for Best Actress in a Supporting Role in 1948.
Cloris Leachman won the Oscar for Best Actress in a Supporting Role in 1971.