Bentonite clays have unique properties that determine their use as the main component of engineered barrier systems (EBS) for the isolation of radioactive waste. At present, the Russian Federation is elaborating the concept of deep geological disposal of radioactive waste in crystalline rocks of the Yeniseisky site, where bentonite clays play an important role in ensuring the safety of the repository for a long period of time. This work demonstrates the first results of short-term laboratory experiments (1 and 3 months) on the thermochemical interaction of bentonite and concrete in the presence of synthetic water at an elevated temperature. These experiments will help predict the effect of EBS materials on montmorillonite. Bentonite from the 10th Khutor deposit (Russia) and Portland cement were used in the experiments. At the first stage of the experiments, solutions were obtained after leaching the concrete with a synthetic groundwater solution for 1 month at 90 °C. At the second stage, the interactions of the obtained solutions with bentonite at 90 °C were studied. As a result of the experiments, the processes of concrete leaching were revealed, which changed the composition and acidity (an increase in the pH from 6.1 to 12.1) of the synthetic water and led to an increase in the porosity of the material in contact with the solution. However, no dissolution of montmorillonite was observed, and the changes were quite small. The research results show the high stability of bentonite from the 10th Khutor deposit under model conditions, which was confirmed by modeling. Thus, we can say that at pH ≈ 12 and at elevated temperatures, montmorillonite retains a stable structure for a long time, which is important for ensuring the safety of disposal in general.