We propose a treatment of nitrogen radical irradiation to 4H-SiC surfaces for improving thermally grown SiO2/SiC interfaces. X-ray photoelectron spectroscopy (XPS) analyses revealed that a 1.7-nm-thick nitride film was formed by nitrogen radical exposure for 30 min and that Si-N bonds were retained after subsequent 10 min oxidation. It was also confirmed by secondary ion mass spectrometry (SIMS) that nitrogen atoms were piled up at the SiO2/SiC interface for the samples fabricated by thermal oxidation for 3 min with nitrogen plasma exposure. The metal-oxide-semiconductor (MOS) capacitors with a thin oxynitride layer formed by nitrogen radical exposure to the SiC surface and subsequent thermal oxidation exhibited excellent capacitance-voltage (C-V) characteristics. The interface state density (Dit) was significantly reduced by nitrogen radical exposure even at the shallow energy level near the conduction band edge. A minimum Dit value of 1.4 × 1011 cm-2eV-1 at Ec – E = 0.44 eV was achieved. Therefore, we can conclude that the treatment of nitrogen radical irradiation to the SiC surface prior to thermal oxidation is a promising method for improving SiC-MOS characteristics.