Jacqueline Zwambila rejected assurances from the Zimbabwean government that it is safe for her to return home, saying she is the victim of a smear campaign because she is aligned with the opposition party Movement for Democratic Change.
"We [party members] are always under attack from the government of the present regime," the Australian Broadcasting Corp. quoted her as saying in Canberra.
Zwambila was appointed ambassador in 2009 after Zimbabwe's power-sharing government was established.
Opposition leader Morgan Tsvangirai was chosen as prime minister with Robert Mugabe as president. The arrangement ended after July 2013 elections in which Mugabe, in power for 33 years, was re-elected to a five-year term. The Movement party then lost its ministerial posts.
Zwambila has left the embassy, the ABC said, and was awaiting the processing of her application for protection.