Abstract The oxides and nitrides of boron show great potential for use as hard, wear-resistant materials. However, large intrinsic stresses and poor adhesion often accompany the hard coatings as found for the cubic boron nitride phase. These effects may be moderated through the use of a layered structure. Alternate stiff layers of boron (B) and compliant layers of hexagonal boron nitride (hBN) are formed by modulating the sputter gas composition during deposition from a pure B target. The B/hBN thin films are characterized with transmission electron microscopy to evaluate the microstructure, nanoindentation to measure hardness and X-ray absorption spectroscopy to determine chemical bonding. The effects of layer pair spacing on chemical bonding and hardness are evaluated for the B/hBN films.