This paper studies the electronic properties of MOS capacitors fabricated on double positioning boundary free 3C-SiC/6H-SiC where the 3C-SiC films were grown using the Vapour- Liquid-Solid mechanism. The temperature- and frequency-dependent electrical properties of SiO2/3C-SiC/6H-SiC structures have been studied. Capacitance measurements indicate that the single-domain 3C-SiC film is doped near the surface with an average concentration of 8.3 × 1016 cm-3. The measured interface state density near the conduction band edge of 3C-SiC is below 1011cm-2⋅eV-1 and increases towards mid-gap as obtained from conductance and capacitance measurements. Our results are consistent with the assumption that the interfaces of SiO2/ n-type SiC consist of two different kinds of interface traps – the carbon clusters located at the interface and the intrinsic defects located within the oxide layer.