The structure of ultrathin amorphous carbon (a-C) films synthesized by filtered cathodic vacuum arc (FCVA) deposition was investigated by high-resolution transmission electron microscopy, electron energy loss spectroscopy, and x-ray photoelectron spectroscopy. Results of the plasmon excitation energy shift and through-thickness elemental concentration show a multilayered a-C film structure comprising an interface layer consisting of C, Si, and, possibly, SiC, a buffer layer with continuously increasing sp 3 fraction, a relatively thicker layer (bulk film) of constant sp 3 content, and an ultrathin surface layer rich in sp 2 hybridization. A detailed study of the C K-edge spectrum indicates that the buffer layer between the interface layer and the bulk film is due to the partial backscattering of C+ ions interacting with the heavy atoms of the silicon substrate. The results of this study provide insight into the minimum thickness of a-C films deposited by FCVA under optimum substrate bias conditions. Copyright © 2013 Materials Research Society.