This study investigated a two-step thermochemical treatment process consisting of carbonization and halogenation for the removal of radionuclides from spent cation-exchange resin (CER). Based on a thermal analysis of cation-exchange resins, we propose a two-step thermochemical treatment process involving the conversion of spent CER into pyrocarbon and then the removal of radioactive elements from the carbonized CER by converting them volatile halides at very high temperatures. The proposed process mainly consists of a carbonization and halogenation reactor, a UHC (unburned hydrocarbon) combustor, and wet scrubber. A step-by-step experimental and numerical optimization study was conducted with the carbonization and halogenation reactor and the UHC combustor. The optimum operating conditions could be established based on the results of a thermal analysis of the CER, a nonisothermal kinetic analysis, a numerical modeling study of a plug flow reactor (PFR)-type combustor, and a thermodynamic equilibrium analysis of a system consisting of a mix of carbonized CER and halogenation gas. The results of this study present detailed design of a novel multifunctional reactor and operating conditions of a bench-scale carbonization and halogenation process. Basic performance tests using CER doped with nonradioactive Co and Cs, indicated as Cs-137/134 and Co-60/58, were conducted under the optimized conditions. The results of these tests showed that the novel thermochemical process proposed in this study is a viable process that effectively removes radioactive elements from spent CER.