© 2015 Elsevier B.V. One of the most important design variables for a geological nuclear waste repository is the temperature limit up to which the engineered barrier system (EBS) and the natural geologic environment can be exposed. Up to now, almost all design concepts that involve bentonite-backfilled emplacement tunnels have chosen a maximum allowable temperature of about 100. °C. Such a choice is largely based on the consideration that in clay-based materials illitization and the associated mechanical changes in the bentonite (and perhaps the clay host rock) could affect the barrier attributes of the EBS. However, existing experimental and modeling studies on the occurrence of illitization and related performance impacts are not conclusive, in part because the relevant couplings between the thermal, hydrological, chemical, and mechanical (THMC) processes have not been fully represented in the models. This paper presents a fully coupled THMC simulation of a nuclear waste repository in a clay formation with a bentonite-backfilled EBS for 1000. years. Two scenarios were simulated for comparison: a case in which the temperature in the bentonite near the waste canister can reach about 200. °C and a case in which the temperature in the bentonite near the waste canister peaks at about 100. °C.The model simulations demonstrate some degree of illitization in both the bentonite buffer and the surrounding clay formation. Other chemical alterations include the dissolution of K-feldspar and calcite, and precipitation of quartz, chlorite, and kaolinite. In general, illitization in the bentonite and the clay formation is enhanced at higher temperature. However, the quantity of illitization is affected by many chemical factors and therefore varies a great deal. The most important chemical factors are the concentration of K in the pore water as well as the abundance and dissolution rate of K-feldspar less important ones are the concentration of sodium and the quartz precipitation rate. In our modeling scenarios, the calculated decrease in smectite volume fraction in bentonite ranges from 1 to 8% of the initial volume fraction of smectite in the 100. °C scenario and 1-27% in the 200. °C scenario. Chemical changes in the 200. °C scenario could also lead to a reduction in swelling stress up to 15-18% whereas those in the 100. °C scenario result in about 14-15% reduction in swelling stress for the base case scenario. Model results also show that the 200. °C scenario results in a much higher total stress than the 100. °C scenario, mostly due to thermal pressurization. While cautions should be taken regarding the model results due to some limitations in the models, the modeling work is illustrative in light of the relative importance of different processes occurring in EBS bentonite and clay formation at higher than 100. °C conditions, and could be of greater use when site specific data are available.