Extensive studies have been conducted on thermal conductivity of bentonite buffer materials, as it affects the safety performance of barriers engineered to contain high-level radioactive waste. Bentonite is composed of several minerals, and studies have shown that the difference in the thermal conductivity of bentonites is due to the variation in their mineral composition. However, the specific reasons contributing to the difference, especially with regard to the thermal conductivity of bentonites with similar mineral composition, have not been elucidated. Therefore, in this study, bentonites with significantly different thermal conductivities, but of similar mineral compositions, are investigated. Most bentonites contain more than 60% of montmorillonite. Therefore, it is believed that the exchangeable cations of montmorillonite could affect the thermal conductivity of bentonites. The effect of bentonite type was comparatively analyzed and was verified through the effective medium model for thermal conductivity. Our results show that Ca-type bentonites have a higher thermal conductivity than Na-type bentonites.