This study introduces the development of new supercritical water oxidation(SCW)(multiple step oxidation) to destruct recalcitrant organic substances totally and safely by using sodium nitrate as an oxidant. This method has solved the problems of conventional SCW, such as precipitation of salt due to lowered permittivity, pressure increase following rapid rise of reaction temperature, and corrosion of reactor due to the generation of strong acid. Destruction condition and rate in the supercritical water were examined using Polyvinyl Chloride(PVC) and ion exchange resins as organic substances. The experiment was carried out at 450℃ for 30 min, which is relatively lower than the temperature for supercritical water oxidation (600-650℃). The decomposition rates of various incombustible organic substances were very high [PVC(87.5%), Anion exchange resin(98.6%), Cationexchange resin(98.0%)]. It was observed that hetero atoms existed in organic compounds and chlorine was neutralized by sodium (salt formation). However, relatively large amount of sodium nitrate (4 equivalent) was required to raise the decomposition ratio. For complete oxidation of PCB was intended, the amount of oxidizer was an important parameter.