Dame Marie Bashir died aged 95 on January 20, prompting widespread praise for her life of faithful service to the community.
Her funeral will be held at Sydney's St James' Church on Wednesday morning, with many dignitaries expected to turn out to pay their respects for her contribution to the state.
Premier Chris Minns reflected on Dame Marie's ascension to the governorship in 2001, relaying she was "awestruck" and doubted her suitability for the role.
"This was the oldest public office in Australia, held by the likes of Arthur Phillip and Lachlan Macquarie ... she would be the first woman to hold the office and the first person of Lebanese descent," he said on Tuesday.
"I'm told, she then reflected on what her mother would have said if she'd known that Dame Marie would get this offer, and the answer was, pull your socks up and do it for the people."
Her exit from the role in 2014 was similarly humble, quitting before she claimed the title of NSW's longest-serving governor and took it from war hero and Victoria Cross recipient Sir Roden Cutler.
"This was not someone who served for fame or public recognition, for the honours or the awards," Mr Minns said.
Dame Marie was born to a Lebanese father and a mother of Lebanese descent in Narrandera, a town on the banks of the Murrumbidgee River.
She worked at two Sydney hospitals, moved into general practice, then switched to specialise in psychiatry, where she drove mental health reform including establishing psychiatric services for young people and taking a clinical professorship at the University of Sydney.
Dame Marie was the wife of former Sydney lord mayor and legendary Wallabies captain Sir Nicholas Shehadie.
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