The interpretation of the surface chemical states of amorphous boron carbide films as revealed by X-ray photoelectron spectroscopy (XPS) is investigated in this work. Films were deposited by dc-magnetron sputtering and characterized by XPS employing sputter-cleaning and angle-resolved detection. Our results indicate that the intrinsic chemical states of boron carbide occur at ∼282.8 and ∼188.6.eV in the C 1s and B 1s lines, respectively, and that all other observed states are related to contamination due to exposure to ambient conditions. Structural modifications known to occur due to post-deposition annealing could not be observed by XPS, pointing to limitations of this technique.