[2][3] Moloney's first acting experience was with the Merilyn Brend Children's Teenagers and Adults Theatre Company in outer-eastern Melbourne when he was ten years old.

His first role in a feature film was playing a thug in Say a Little Prayer (1993),[2] based on the Robin Klein novel Came Back to Show You I Could Fly.

[7] In April 2004 he was nominated for a Golden Rose of Montreux award for Best Actor in a Soap for his work in Neighbours.

[9] That same year, he appeared with his former Neighbours co-star, Mark Little, in an episode of Celebrity Wedding Planner broadcast on 3 September 2012.

[3] On 27 June 2024, Moloney announced that he would be leaving Neighbours after playing Toadie for almost 30 years.

[21] In September 2024, Moloney embarked on a one-man show around the UK called Toad on the Road.

[23] Moloney is an active patron of the Down Syndrome Association of Victoria,[2] and has been involved with the Victorian Police Department's Films For Schools Youth project.[2][when?]

[2] In 2010, Moloney became a spokesman for weight loss company Lite and Easy, successfully losing 17 kg in 13 weeks.