The Korea government decided to shut down Kori-1 and Wolsung-1 nuclear power plants (NPPs) in 2017 and 2019, respectively, and their decommissioning plans are underway. Decommissioning of a NPP generates various types of radioactive wastes such as concrete, metal, liquid, plastic, paper, and clothe. Among the various radioactive wastes, we focused on radioactive-combustible waste due to its large amount (10,000–40,000 drums/NPP) and environmental issues. Incineration has been the traditional way to minimize volume of combustible waste, however, it is no longer available for this amount of waste. Accordingly, an alternative technique is required which can accomplish both high volume reduction and low emission of carbon dioxide. Recently, KAERI proposed a new decontamination process for volume reduction of radioactivecombustible waste generated during operation and decommissioning of NPPs. This thermochemical process operates via serial steps of carbonization-chlorination-solidification. The key function of the thermochemical decontamination process is to selectively recover and solidify radioactive metals so that radioactivity of the decontaminated carbon meets the release criteria. In this work, a preliminary version of mass flow diagram of the thermochemical decontamination process was established for representative wastes. Mass balance of each step was calculated based on physical and chemical properties of each constituent atoms. The mass flow diagram provides a platform to organize experimental results leading to key information of the process such as the final decontamination factor and radioactivity of each product.