The National Library incorporates major works of art that have become closely associated with the building. As the concept for the Library’s building developed, the chief architect, Walter Bunning (1912-1977), made the suggestions for initial artworks, believing they should reflect the classical style of the architecture. Most of these works of art were commissioned by Bunning around the time the Library was opened in 1968, and can still be found in the foyer, exterior and grounds of the building.

As the Reading Rooms changed over the years, more artwork was installed in these spaces, displaying some of the unique artwork from the Library's collection, and selected to complement the interior design and intended usage of these rooms.

The Main Reading Room showcases artwork that is inspired by Indigenous stories of the Australian landscape. The Special Collections Reading Room houses art focusing on modern Australian people and places. On the Third Floor, the Asian Collections Reading Room displays a range of artwork representing the cultures of many of Australia's regional neighbours.