She proposed the Flora and Fauna Guarantee Act 1988, the first Australian legislation which gave legal protection of rare species.

When Cain resigned after a collapse in his political support in August 1990, Kirner was elected Labor leader and thus became Victoria's first female Premier.

The party hoped that the elevation of a popular woman as its new leader would improve its position, but Kirner never succeeded in gaining control of the crisis into which the state had plunged.

The conservative-leaning Melbourne newspaper, the Herald Sun, reacted unfavourably to a Premier from the Socialist Left, dubbing her "Mother Russia".

Although she remained personally more popular than the Liberal Opposition Leader, Jeff Kennett, it was not nearly enough to overcome Victorians' growing anger at Labor.

The Coalition's "Guilty Party" campaign did much to stoke this anger, targeting many Ministers in the Kirner Government and providing examples of concerns in their portfolios.

The campaign attracted controversy with ALP ads stating that if the Liberals won the election it would institute the same policies that were implemented in New Zealand by the then Fourth National Government.

New Zealand Prime Minister Jim Bolger responded in reference to the campaign, "You know, they say that the show’s never over until the fat lady sings.

[9] A portrait of Kirner painted by Adelaide artist Annette Bezor in 1994[10] hangs in Queen's Hall at Parliament House Victoria.

Subsequently, she devoted her energies to the Australian affiliate of EMILY's List Australia, an organisation which promotes pro-choice women's careers in politics.

Kirner was one of the leaders of the movement in the Labor Party to adopt a policy of setting targets for the number of women candidates in winnable electorates.

[11] In 1993, she famously appeared on The Late Show with colleague David White, MLC for Doutta Galla, in a musical skit performing Joan Jett's "I Love Rock 'n' Roll".

[16] On 11 June 2012, she was named a Companion of the Order of Australia for "eminent service to the Parliament of Victoria and to the community through conservation initiatives, contributions to gender equality, the development of education and training programs and the pursuit of civil rights and social inclusion.