Globally, the operation of nuclear power plants results in the production of a tremendous quantity of spent nuclear fuel. The methods for handling spent nuclear fuel can be categorized into three: storage, direct disposal and recycling. A technology designed to recycle accumulated spent nuclear fuel is pyropocessing. In pyroprocessing, various fission products (FPs) such as C-14, H-3, I-129 and Cs-137 are generated. Among these FPs, technetium (Tc-99) is a gaseous nuclear isotope with a long half-life and high mobility in the form of TcO4 - in aqueous solutions, making it essential to capture strictly in order to prevent radioactive contamination of the environment. In previous studies, ion-exchange or adsorption using MOFs (Metal Organic Frameworks) have been used to remove Tc-99. These methods, however, involve separation in aqueous solutions, not in the gaseous state. In this study, we developed a CaO-based adsorbent for capturing Re as a surrogate for radioactive Tc-99. Isopropyl alcohol (IPA) was employed as a pore-forming agent during the preparation of the adsorbents, and its effects on characteristics and adsorption performance were investigated. The size of the pores were analyzed from nitrogen (N2) adsorption isotherm analysis and mercury (Hg) intrusion curves. As a result, it was confirmed that the addition of IPA had a significant impact on the formation of macro-pores. Furthermore, this macroporous structure was found to enhance the adsorption performance of Re.