Low-temperature post-oxidation annealing (POA) process of high-reliability thermal oxides grown on 4H-SiC using new apparatus that generates atomic hydrogen radicals by high-temperature catalyzer has been investigated. Atomic hydrogen radicals were generated by thermal decomposition of H2 gas at the catalyzer surface heated at high temperature of 1800°C, and then exposed to the sample at 500°C in reactor pressure of 20 Pa. The mode and maximum values of field-to-breakdown are 11.0 and 11.2 MV/cm, respectively, for the atomic hydrogen radical exposed sample. In addition, the charge-to-breakdown at 63% cumulative failure of the thermal oxides for atomic hydrogen radical exposed sample was 0.51 C/cm2, which was higher than that annealed at 800°C in hydrogen atmosphere (0.39 C/cm2). Consequently, the atomic hydrogen radical exposure at 500°C has remarkably improved the reliability of thermal oxides on 4H-SiC wafer, and is the same effect with high-temperature hydrogen POA at 800°C.