We report on a novel method for epitaxial 3C-SiC growth on Si, achieved by annealing of a high-quality SiO2/Si structure in a CO containing gas ambient. In this way high quality epitaxial 3C-SiC seeds are produced on Si (001) surfaces. The SiC crystallites grow into the Si surface layer without voids at the Si/SiC interface. So far a 20% SiC coverage of the Si surface has been achieved with some SiC crystallites coalescing without grain boundaries. The system has been investigated by TEM (Transmission Electron Microscopy) and CV (Capacitance-Voltage) measurements.