Hetero-interface properties of SiO2/4H-SiC on (0001), (11-20), and (03-38) crystal orientations are presented. Epitaxial growth on new crystal orientations, (11-20) and (03-38), is described by comparing with the growth on (0001). Using thermal oxidation with wet oxygen, metal-oxide-SiC (MOS) structure was fabricated. From high-frequency capacitance-voltage characteristics measured at 300 K and 100 K, the interface properties were characterized semi-quantitatively. The interface state density was precisely determined using the conductance method for the MOS structure at 300 K. The new crystal orientations have the lower interface state density near the conduction band edge than (0001). From the characteristics of inversion-type planar MOSFETs, higher channel mobilities were obtained on (03-38) and (11-20) than on (0001). The cause of the difference in the channel mobility is speculated by the difference bond configuration of the three crystal orientations.