[4][5] In March 1974, before leaving the Young Talent Time regular cast, Byrne released her first solo single, "He's a Rebel", a cover version of the Phil Spector-produced 1962 hit by the Crystals.

[4] Her debut album, She's a Rebel (1974), was produced by Young, with session musicians including Russell Dunlop on drums (ex-Aesops Fables, SCRA, Renée Geyer and Mother Earth, Johnny Rocco Band), Tim Partridge on bass guitar (Company Caine, Mighty Kong, Kevin Borich Express), Mark Punch on guitar (Johnny Rocco Band, Renée Geyer Band) and Terry Walker on guitar and backing vocals (the Strangers, Pastoral Symphony).

[4][9] In September 1975 Byrne travelled to London to record at Abbey Road Studios with Cliff Richard producing.

[4] Byrne's first Australian television guest appearance as a featured solo artist was on The Graham Kennedy Show at the age of fifteen.

[10] Craig Walsh of The Australian Women's Weekly previewed a segment for a rock 'n' roll themed episode, "[its] staging promises to make the series the smash hit of 1980, say the producers" with Byrne declaring "I've just discovered I can dance better than I thought.

[4] She made a successful and highly publicised career comeback in 1985 with the starring role as Kathy McLeod, opposite Matt Dillon, in the feature film, Rebel.

[14] Byrne sang lead vocals on nine of ten tracks on Rebel: Original Motion Picture Soundtrack (1985).

[18] The show also starred Wendy Stapleton and Lisa Edwards (replaced by Nikki Nicholls) as a tribute to the Supremes, Cilla Black, Dusty Springfield, Patsy Cline and Lulu.

Since 1972 Byrne has been a regular performer at the Christmas Eve Carols by Candlelight concert at Melbourne's Sidney Myer Music Bowl.

At the 2005 concert she performed a duet of Silent Night with her five-year-old daughter, Lucille, who was making her professional stage and television debut.

"[23] Byrne reprised her role of Grizabella in the ExitLeft production of Cats, which was staged at the Derwent Entertainment Centre in Hobart in late-October 2007.

[25][26][27] From 29 July 2010 to April 2011 she played the role of the Bird Woman in the original Australian production of the stage musical, Mary Poppins at Melbourne's Her Majesty's Theatre.

"[32] In 2016 she took the role of Carlotta Campion in a concert version of Follies at the Melbourne Recital Hall for a limited run of three performances in May.

In mid 2019, she is set to play the Beggar Woman in a production of Sweeney Todd: The Demon Barber of Fleet Street opposite Anthony Warlow and Gina Riley.

[38] During her stint in Young Talent Time Byrne had a sexual relationship with "Michael", an on-set boom-camera operator: she was under-age and he was more than ten years older.

The attitude was, 'It's over now, it's finished', but this was personal and embarrassing and humiliating and distressing ... Parents need to be aware that even now, with the best protections in place, there's going to be someone who cares more for the product than the child.

[40] Byrne described how "I was drinking, smoking, barely eating, and spending a lot of time in hotel rooms fighting anxiety and depression.

"[41] Later she recalled meeting Dudley at a party where her "latest boyfriend was an everyday dope smoker and I loved the freedom the drug gave me.

During 1987 while rehearsing for her role of Fantine in the Australian theatre production of Les Misérables, Byrne met fellow actor, Neil Melville.

[46] In March 1998 she told Peter Ford of Playbill that "Nobody ever bothered to investigate if that was my major problem, when finally I had a label for my troubles it was a great relief.

"[46] Byrne was the domestic partner of French musician, Ced Le Meledo, with whom she collaborated on the live show, Paris-Melbourne.

[47] In that same year her autobiography, Not Quite Ripe: A Memoir, was released and described by her publisher as "the real story of her gritty, sometimes perilous existence as she chased her career, became addicted to heroin and finally rehabilitated herself".