The long-time Labor senator for South Australia was a minister in the Hawke and Keating governments, first elected in 1980 and only retiring in 2005.
The son of Greek immigrants, he was appointed consumer affairs minister in the Hawke government in 1988 and served as immigration and ethnic affairs minister from 1993-96 in the Keating administration.
Prime Minister Anthony Albanese on Thursday paid tribute to one of Labor's "great sons" who he said held true to his principles and sense of purpose throughout a distinguished career.
"Nick was both a strong advocate for the benefits and contribution of modern, multicultural Australia and a compelling example of how our nation has been enriched by people of every background and tradition."
South Australian Premier Peter Malinauskas said Mr Bolkus was one of Labor's "great champions" and had died peacefully on Christmas morning.
"Nick was deeply respected across the political divide," the premier said in a statement.
"He was a formidable intellect, a tireless advocate for the Labor Party and a generous mentor to many. He was much loved by his family, colleagues and friends."
Mr Malinauskas said he had sent his condolences to Mr Bolkus's wife Mary and daughters Mikayla and Aria, the latter a candidate for SA Labor at the upcoming 2026 state election.
As immigration minister Mr Bolkus allowed thousands of Chinese nationals who arrived in Australia before the 1989 Tiananmen Square massacre in Beijing to permanently settle, along with their relatives.
In his valedictory speech to parliament in 2005 Mr Bolkus said his proudest achievement in politics was letting 40,000 asylum seekers stay permanently.
"The sky didn't come crashing down. The hordes didn't invade," he said.
Mr Bolkus was a lawyer and research officer before entering parliament.
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