To achieve permanent disposal of radioactive waste drums, the radionuclides analysis process is essential. A variety of waste types are generated through the operation of nuclear facilities, with dry active waste (DAW) being the most abundant. To perform radionuclides analysis, sample pretreatment technology is required to transform solid samples into solutions. In this study, we developed a dry ashing-microwave digestion method and secured the reliability of the analysis results through a validity evaluation. Additionally, we conducted a comparative analysis of the radioactivity of 94Nb nuclides with and without the chemical separation process, which reduced the minimum detectable activity (MDA) level by more than 65-fold for a certain sample.