In the decommissioning process of nuclear power plants, Ni-59, Ni-63 and Fe-55 present in radioactive waste are crucial radionuclides used as fundamental indicators in determining waste treatment methods. However, due to their low-energy emissions, the chemical separation of these two radionuclides is essential compared to others. Therefore, this study aims to evaluate the suitability of various pre-treatment methods for decommissioning waste materials by conducting characteristic assessments at each chemical separation stage. The goal is to find the most optimized pre-treatment method for the analysis of Ni-59, Ni-63 and Fe-55 in decommissioning waste. The comparative evaluation results confirm that the chemical separation procedures for Fe and Ni are very stable in terms of stepwise recovery rates and the removal of interfering radionuclides. However, decommissioning waste materials, which mainly consist of concrete, metals, etc., possess unique properties, and a significant portion may be low-radioactivity waste suitable for on-site disposal. Considering that the chemical behavior and reaction characteristics may vary at each chemical separation stage depending on the matrix properties of the materials, it is considered necessary to apply cascading chemical separation or develop and apply individual chemical separation methods. This should be done by verifying and validating their effectiveness on actual decommissioning waste materials.