The former Nationals leader died peacefully in the Heritage Lodge aged-care home in Murwillumbah, north-east NSW, on Sunday morning, his family said in a statement.
Mr Anthony was leader of the Country Party/National Party for 12 years and deputy prime minister for nearly 10, influencing coalition policies for much of the 1970s and 1980s.
He served under six prime ministers, starting with Sir Robert Menzies.
Prime Minister Scott Morrison said Mr Anthony "was a man with no pretences who was passionate about regional Australia".
As primary industry minister, he established the Australian Wool Corporation, Mr Morrison said.
“As trade and resources minister, Doug worked to modernise and expand our trade agreement with New Zealand, opened up the uranium industry in Australia, and sought to expand trade with Japan, China and the Middle East,” he said.
Deputy Prime Minister Michael McCormack said "rural and regional Australia has lost one of our greatest today".
“The outcomes Doug Anthony secured for regional and rural Australia have stood the test of time,” the current Nationals leader said.
“He was dedicated to ensuring country Australians had a strong voice in government and that they were not just listened to, but that they were front of mind for government decision-makers.”
He was a man of "decency, integrity, purpose and resolve", Mr McCormack said.
“Tales of him in the capacity of acting prime minister and leading the country from his caravan on the NSW north coast make up the political fabric of our party and our nation.”
Nationals deputy leader David Littleproud said Mr Anthony epitomised the finest qualities of leadership and service, leaving a significant legacy for future generations of National Party representatives to uphold.
Among others to pay tribute, former prime minister Malcolm Turnbull described Mr Anthony as "a great Australian".
“An eloquent and committed advocate for an Australian republic often sharing a platform with his Liberal partner Malcolm Fraser and their old Labor rivals Gough Whitlam and Bob Hawke,” Mr Turnbull tweeted.
Mr Anthony is survived by his wife Margot, his three children and nine grandchildren.
The family statement said they were tremendously proud of his legacy.
“While always very humble, he made a lasting contribution to the nation, and particularly to people in country Australia.”
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