High quality single crystal SiC films were prepared by carbonization of polyimide Langmuir-Blodgett films on Si substrate. The films formed after annealing of the polyimide films at 1000°C, 1100°C, 1200°C were studied by Fourier transform-infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, transmission electon microscopy (TEM), transmission electron diffraction (TED), and scanning electron microscopy (SEM). XRD study and HRTEM cross-section revealed that the crystalline SiC film begins to grow on Si (111) substrate at 1000°C. According to the HRTEM cross-section image five planes in 3C-SiC (111) film are aligned with four Si(111) planes at the SiC/Si interface. It was shown the SiC films (35 nm) grown on Si(111) at 1200°C have mainly cubic 3C-SiC structure with a little presence of hexagonal polytypes. Only 3C-SiC films (30 nm) were formed on Si (100) substrate at the same temperature. It was shown the SiC films (30-35 nm) are able to cover the voids in Si substrate with size up to 10 μm.