Cubic boron nitride (c-BN) has potential for electronic applications as an electron emitter and serving as a base material for diodes, transistors, etc. However, there has been limited research on c-BN reported, and many of the electronic properties of c-BN and c-BN interfaces have yet to be reported. This dissertation focused on probing thin film c-BN deposited via plasma enhanced chemical vapor deposition (PECVD) with in situ photoelectron spectroscopy (PES). PES measurements were used to characterize the electronic properties of c-BN films and interfaces with vacuum and diamond. First, the interface between c-BN and vacuum were characterized with ultraviolet PES (UPS). UPS measurements indicated that as-deposited c-BN, H2 plasma treated c-BN, and annealed c-BN post H2 plasma treatment exhibited negative electron affinity surfaces. A dipole model suggested dipoles from H-terminated N surface sites were found to be responsible for the NEA surface. Then, Si was introduced into c-BN films to realize n-type doped c-BN. The valence structure and work function of c-BN:Si films were characterized with XPS and UPS measurements. Measurements were unable to confirm n-type character, and it is concluded that silicon nitride formation was the primary effect for the observations. Finally, XPS measurements were employed to measure the band offsets at the c-BN/diamond interface. Measurements indicated the valence band maximum (VBM) of c-BN was positioned ~0.8 eV above the VBM of diamond.