The effects of the crystal quality and surface morphology on the electrical properties of MOS capacitors have been studied in devices manufactured on 3C–SiC epitaxial layers grown on silicon (1 0 0) substrate. The interface state density, which represents one of the most important parameters, has been determined through capacitance measurements. A cross-correlation between high resolution X-ray diffraction, AFM analysis and electrical conductance measurements has allowed to determine the relationship between the crystalline quality and the interface state density. A decrease of the interface state density down to about 1011 cm−2 eV−1 was observed with improving the crystalline quality.