Australia is the latest addition to the list of countries who recognise Venezuelan opposition leader Juan Guaido as interim president.
Foreign Minister Marise Payne has confirmed that Australia stands with the United States and major European powers against President Nicolas Maduro.
"Australia recognises and supports the President of the National Assembly, Juan Guaido, in assuming the position of interim president, in accordance with the Venezuelan constitution and until elections are held," Senator Payne said in a statement.
"We now urge all parties to work constructively towards a peaceful resolution of the situation, including a return to democracy, respect for the rule of law and upholding of human rights of the Venezuelan people."
Maduro, 56, is confronting an unprecedented challenge to his authority after Guaido declared himself interim president.
Guaido has won wide international support, and is now calling on his supporters to stage peaceful protests on Wednesday to ask for humanitarian aid to be allowed into the country.
Guaido also called on people from across Venezuela and from "all over the world" to hold mass demonstrations on Saturday to coincide with an ultimatum given by the European Union to plan new elections.
Maduro says Guaido is taking part in a coup directed by US President Donald Trump's advisers.
"Nobody respects the weak, cowards, traitors. In this world what's respected is the brave, the courageous, power," Maduro said.
The government on Sunday began a publicity campaign online based on the slogan "Always Loyal, Never a Traitor."
Maduro also rejected the European ultimatum and said Guaido violated the constitution by declaring himself interim leader.
"Fortunately, we don't depend on Europe ... the leaders of Europe are sycophants, kneeling behind the policies of Donald Trump," he told CNN.
White House national security adviser John Bolton warned on Sunday against violence or intimidation of American diplomats in Venezuela or Guaido, saying such action would trigger a response from the United States.
Maduro has denounced an alleged conspiracy aimed at spreading rebellion in the army, saying thousands of messages were being sent to soldiers every day over social media from neighbouring Colombia.
Guaido also sent a message to the military on Sunday, asking for their support and ordering them not to repress civilians during an event in which supporters handed out copies of a proposed amnesty for people accused of crimes in the Maduro government.
"I order you not to shoot," he said. "I order you not to repress the people."
At the United Nations Security Council on Saturday, Russia and China strongly backed Maduro and rejected calls by the US and others for early elections.
Both countries are major creditors to Venezuela.
