It is well known that the structure (morphology and crystallography) and composition of physical vapour deposited metallic and hard ceramic coatings can vary significantly with the process deposition variables, which in turn may influence the physical, chemical and mechanical properties of the coatings. In the present study, the crystallographic nature of magnetron-sputtered Nb coatings deposited on 316L stainless steel substrates using reflection high-energy electron diffraction was assessed as a function of the substrate bias voltage, argon gas pressure, deposition rate and film thickness. Generally, Nb coatings showed a one degree preferred orientation, the direction of orientation being largely influenced by the substrate bias voltage, and to a lesser extent by the other parameters. Here, mixtures of polycrystalline, {222}-, {211}- and {200}-orientated structures were observed, varying in both intensity and degree of orientation, depending on the combination of the selected deposition parameters used.