His death, on Monday after a recent serious battle with double pneumonia, was marked by tolling church bells and preparations for scores of memorial masses for the Catholic figurehead.
It may also prove a turning point in Australia's relationship with the Vatican after Francis overlooked local archbishops when selecting the nation's sole cardinal last December.
Cardinal Mykola Bychok said he was filled with sadness for the loss of a "pope of peace" and a man of simple piety.
"This sadness is our human reaction to the death of a much-loved father," the Ukrainian-born Melbourne cardinal said.
"I am grateful for the late Holy Father's frequent appeals for a just peace in Ukraine and for the efforts of the Holy See that he oversaw - known and secret - that in some way helped bring relief to the imprisoned and suffering."
Cardinal Bychok was on his way to the Middle East on a pilgrimage but will divert to Rome as soon as practicable.
He will take part in the funeral rites before joining other cardinal electors to choose the 267th and next Pope.
Archbishop of Sydney Anthony Fisher - who was controversially overlooked as cardinal - praised the pontiff's condemnation of what he described as 'the globalisation of indifference' when it came to refugees and the poor and 'the throwaway culture' towards the unborn and elderly.
"Pope Francis passionately decried views and actions contrary to human dignity and flourishing," he said.
Prime Minister Anthony Albanese, a devout Catholic, recalled that the first Pope from the southern hemisphere had compassion that embraced all of humanity.
Joining the prime minister in private prayer at Melbourne's St Patrick's Cathedral on Monday evening, Mary Picard recalled a "really good" and progressive Pope.
"He did a lot of good, making some of the really sort of high ceremonies a bit more ... for the people," she told AAP.
Opposition leader Peter Dutton noted the late Pope lived frugally, simply and was driven by "Christ's values of mercy and forgiveness".
Pope Francis was also lauded for inspiring Australia's 820,000 Catholic school students to live with courage and compassion.
"His legacy will continue to guide our work in Catholic schools and shape the hearts and minds of students for generations to come," National Catholic Education Commission executive director Jacinta Collins said.
While not without controversy, his papacy was marked by an emphasis on the mercy and compassion of God, and on the Church's vocation to be a sign and bearer of that merciful love in an increasingly troubled world, Australian Catholic Bishops Conference president Archbishop Timothy Costelloe said.
The change in leadership could also offer a chance for Australia to "reset" its relationship with the Vatican, Deakin and Oxford universities' Catholic Church historian Miles Pattenden said.
"It was an extraordinary snub that Francis made Mykola Bychok, the Ukrainian Australian Bishop, cardinal and not the Archbishop of Sydney (Fisher)," Dr Pattenden told AAP.
"There's no way to read that, except as a rebuke to Sydney. It may be that a new Pope allows for a re-test of that, even if he's still a liberal."
Parishes around the country are expected to hold special memorial masses for the late Pope in coming days.
National flags on federal government buildings will fly at half-mast on Tuesday as a mark of respect.
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