About 400 pieces will go on show from Friday, including those worn and owned by the likes of Elizabeth Taylor, Grace Kelly, Princess Margaret and the Duchess of Windsor.
"This is by far the largest show we've ever done on jewellery. It is truly epic," said senior NGV curator Amanda Dunsmore.
The exhibition was originally staged at London's Victoria & Albert Museum in collaboration with Cartier, but the Melbourne version is significantly larger, including archival material and additional Australian elements.
There's a whole case of jewels worn by opera singer Dame Nellie Melba, and a display of opals with rare black gems from Lightning Ridge in NSW.
Cartier kangaroo ornaments are the result of a fashion for animals rendered in stones at the start of the 20th century, and there's even a watch with a koala inlaid on its face in straw.
The jewellery house was founded in 1847 by Louis-Francois Cartier.
Under his grandsons Louis, Pierre and Jacques Cartier, it expanded internationally during the 1920s, becoming a global luxury giant.
For gallery-goers concerned the NGV has strayed too far into the commercial territory of luxury brands, Dunsmore says the gallery is presenting works of the highest quality and design intent.
"From our perspective, it is really about exceptional design, and the craftsmanship and technical innovation of these pieces," she said.
Cartier runs until October 4 at the NGV.
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