The structure of 3 nm and 15 nm diamond-like carbon films, grown on Si(001) by filtered cathodic arc, was studied by angle-resolved X-ray photoelectron spectroscopy (ARXPS) and transmission electron microscopy (TEM). The ARXPS data was deconvolved by employing simultaneous-fitting, which allowed for a clear deconvolution of the Si 2p and C 1s spectra into their different chemical contributions. An analysis of the take-off angle dependence of the peak intensities allowed for an independent identification of the physical origin of the chemical species. It was shown that the C 1s peak at 283.3 eV and the Si 2p peak at 99.6 eV correspond to SiC, and that the C/Si interface of the 3 nm film consists of a stoichiometric approximately 1 nm SiC layer. To quantify the sp(3)-sp(2) ratio it was necessary to take into account not only their associated C 1s XPS-peak intensities, but also their take-off angle dependence. The thickness of the films obtained through ARXPS closely agrees with cross-sectional TEM images.