The venue, part of the $344 million Sydney Modern Project, is the most significant cultural development in the city since the opening of the Opera House in 1973.
More than 15,000 people are registered to attend on the opening weekend alone.
On their way to the SANAA-designed pavilions, many will head past the old building, which began construction in 1896 and has been extended several times since.
The contrasts between the sandstone edifice and the light-filled spaces of its new neighbour are striking and speak to how much the Australian art world has changed with time.
On the old building the patriarchy is literally set in stone, with the names of 32 painters, sculptors and architects arrayed atop its columns - all of them men.
From Raphael and Rembrandt to da Vinci and Velazquez, the neoclassical building was designed as a temple to art, and women were simply not in the frame.
But the names of those artists were hugely aspirational in the Australian art world at the time, according to Art Gallery of NSW deputy director Maud Page.
"They wanted to be the best and they put up the names that they knew, but none of them were women," she told AAP.
In the new building, 53 per cent of the art inside is by female artists.
Curators never set out to reach any targets, according to Ms Page.
"Our principles were that we wanted more female stories on the wall, but it was never forced ... we did the counting afterwards," she said.
In the relocated Yiribana Gallery of Aboriginal and Torres Strait Islander art, there is a majestic installation titled Belonging by Grace Lillian Lee.
Her five sculptures are made using ancient indigenous techniques from cane, wool, cotton and dyed feathers - they are imposing and beautiful, reminiscent of a headdress or armour.
There are four white sculptures and a central red one representing Ms Lee herself.
"Understanding that I can stand strong in knowing that I belong, and to be bold and powerful in who I am," she said.
After 10 years working on Sydney Modern, Ms Page has a sense of achievement and real pride in both the building and its artworks.
"I'm just really happy there can be a place this beautiful to put art, I hope that people really enjoy it as much as we have," she said.
AAP travelled with the assistance of AGNSW.
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