The show, titled Viktor & Rolf: Fashion Artists, is the label's first in Australia.
It brings together pieces from its ready-to-wear collections and installations, including a striped dress embroidered with crystals, a coat with the word "no" stitched into the collar, and a sculptural white headpiece and dress.
The label's ongoing Dolls series – tiny mannequins dressed in miniature versions of well-known Viktor & Rolf looks – is also being shown.
Twenty-one dolls in total are on display, each one handmade. The oldest dates back to 2008, when the designers created the first doll for The House of Viktor & Rolf exhibition at London's Barbican.
Each collection is marked by a new doll, dressed in a key piece.
"With exquisite craftsmanship and dreamy silhouettes, sometimes made from tinkling bells or red carpet, the Dutch fashion artists Viktor & Rolf have been creating wearable art for the past twenty years in a unique, singular style," said the exhibition's curator, Thierry-Maxime Loriot.
In addition to clothes, the gallery has put together runway footage showing the label's often-intricate set designs – several of which have been created by Studio Job.
An exhibition aimed at children is also being hosted at the gallery, focusing on the wedding dress the label created for Princess Mabel of Orange-Nassau.
Younger visitors are encouraged to design their own fashion accessory inspired by the dress, using paper folding and layering.
"Viktor & Rolf stretches the definition of both fashion and art," said the gallery's director Tony Ellwood. "Their boundary-pushing designs challenge the way fashion is developed, presented and disseminated with masterful craftsmanship, intellectual rigour and an ironic sense of humour."
The label's founders Viktor Horsting and Rolf Snoeren set the fashion house up in 1992, and have become known for their "wearable art" philosophy.
Viktor & Rolf's 2016 collection was constructed from shreds of fabric left over from previous seasons.
Viktor & Rolf: Fashion Artists opened at the National Gallery of Victoria on 21 October 2016 and continues until 26 February 2017.