Gaomiaozi (GMZ) bentonite has been recognized as the first choice for using as buffer/backfill materials in deep geological repository for the disposal of high-level nuclear waste (HLW) in China. Groundwater in Beishan area, which has been considered as a potential site for the construction of Chinese deep geological repository, may reach a high pH value because of its chemical background and possible cement degradation during the operation of the repository. Meanwhile, temperature may increase with decay heat released from the waste in the canister. Investigation of pH value of alkaline-solutions and temperature effects on the behavior of compacted GMZ01 bentonite is of great importance for the Chinese deep geological repository program. For this purpose, a series of swelling pressure and hydraulic conductivity tests with various pHs of NaOH solutions were conducted at different temperatures. The X-ray diffraction (XRD) exploration was performed on the GMZ01 bentonite specimens before and after experiencing the swelling pressure and hydraulic conductivity tests, in order to find out the influences of temperature and pHs on the mineralogy of GMZ01 bentonite. Results show that the swelling pressure of GMZ01 bentonite decreases as the pH value of NaOH solutions increases, while the decreasing rate significantly depends on temperature. The swelling pressure evolution curve was “double-peak” structured, which faded with the increases of pH and temperature. The hydraulic conductivity of GMZ01 bentonite increases with the increase of the pH value of NaOH solutions and the rise of temperature. All these observations were consistent with the XRD test results: the dissolution of montmorillonite in GMZ01 bentonite increases with the pH increases. This process was accelerated by the temperature rise.