The Republic of Korea is expected to participate in the denuclearization verification activities by the International Atomic Energy Agency (IAEA) in case any neighboring countries declared denuclearization. In this study, samples for the verification of nuclear activities in undeclared areas were selected for the denuclearization of neighboring countries, and the appropriateness of the procedures was considered. If a country with nuclear weapons declares denuclearization, it must be accompanied by the IAEA’s verification regarding nuclear materials and weapons in the declared and undeclared areas. The analysis of the process samples or on-site environmental samples and the verification of undeclared nuclear facilities and materials aid in uncovering any evidence of concealment of nuclear activity in undeclared areas. Therefore, a methodology was established for effective sampling and analysis in accordance with proper procedures. Preparations for sampling in undeclared areas were undertaken for various potential scenarios, such as, the establishment of zones according to radiation dose, methods of supplying electricity, wireless communication networks, targets of sampling according to characteristics of nuclides, manned sampling method, and unmanned sampling method. Through this, procedures were established for pre- and post-site settings in preparation for hazards and limiting factors at nuclear inspection sites.