It adopts an unusual structure, being cubic as is rock salt structure, but where both niobium and oxygen atoms are four coordinate square planar. The niobium centers are arranged in octahedra, and there is a structural similarity to the octahedral niobium clusters in lower halides of niobium. In NbO the Nb-Nb bond length is 298 pm which compares to 285 pm in the metal. One study of the bonding concludes that strong and nearly covalent bonds exist between the metal centers.
It is a superconductor at 1.38 K. It is used in capacitors where a layer of Nb2O5 is formed around NbO grains as the dielectric.