Abstract We have used X-ray photoemission spectroscopy to study the interaction of gold (Au) with novel boron carbide-based semiconductors grown by plasma-enhanced chemical vapor deposition (PECVD). Both n- and p-type films have been investigated and the PECVD boron carbides are compared to those containing aromatic compounds. In the case of the p-type semiconducting PECVD hydrogenated boron carbide samples, the binding energy of the B(1s) core level shows a shift to higher binding energies as the Au is deposited, an indication of band bending and possibly Schottky barrier formation. In the case of the n-type boron carbide semiconductors the interaction at the interface is more typical of an ohmic contact. Addition of the aromatic compounds increases the change in binding energies on both n-type and p-type PECVD boron carbide semiconductors, and the gold appears to diffuse into the PECVD boron carbides alloyed with aromatic moieties.