To analyze the radioactivity of 3H and 14C in miscellaneous radioactive wastes generated from nuclear power plants, a wet digestion method using sulfuric acid is currently used. However, sulfuric acid is classified as a special management material, and there is no disposal method for contaminated radioactive waste. Therefore, research on a thermal decomposition method that can analyze the DAW radioactive waste samples without using sulfuric acid is necessary. In this study, we will cover the final sample amount, sample injection method, and prevention of organic ignition to meet the minimum detection limit requirements of the analysis equipment. Through this research, optimal conditions for the thermal decomposition method for analyzing the radioactivity of 3H and 14C in DAW radioactive wastes generated from nuclear power plants can be derived.