Feature films
Mercurio made his film debut in Baz Luhrmann's breakout film Strictly Ballroom, receiving an Australian Film Institute Award nomination in 1993. Mercurio was a choreographer on the film. For his performance in Strictly Ballroom, Mercurio was also nominated for an AACTA Award for Best Actor in a Leading Role in 1992, losing to Russell Crowe. Flamenco dancer Antonio Vargas, the actor who played Fran's father, also choreographed scenes in the film.
Mercurio's other film credits include: Exit to Eden, Back of Beyond, Così, Red Ribbon Blues, Welcome to Woop Woop, The Dark Planet, The First 9½ Weeks, Kick and Sydney – A Story of a City. He starred, wrote, choreographed, produced and directed the short film Spilt Milk. Most recently, Mercurio has taken roles in independent films, such as Hunting for Shadows and A Silent Agreement with director Davo Hardy.
In 2019, Mercurio appeared in a supporting role as Sal in Promised (2019), a film directed and co-produced by Nick Conidi, and starring Tina Arena, Antoniette Iesue and Daniel Berini. The film was released in Australia on 24 October 2019.
Baz Luhrmann expressed some interest in using Mercurio in Moulin Rouge to Mercurio's agent, but after a series of failed attempts to speak to Luhrmann personally, Mercurio found out that there was no role for him in the movie via the production company. He has not appeared in any other Luhrmann films and only appears briefly in Disc 4 of Red Curtain Trilogy as a pixelated image.
Concerned about being typecast early on in his film career, Mercurio turned down the role of Adam Whitely (which instead went to Guy Pearce), in the 1994 film, The Adventures of Priscilla, Queen of the Desert.