Pilot sites are currently used to test the performance of bentonite barriers for sealing high-level radioactive waste repositories, but the degree of mineral stability under enhanced thermal conditions remains a topic of debate. This study focuses on the SKB ABM5 experiment, which ran for 5 years (2012 to 2017) and locally reached a maximum temperature of 250 °C. Five bentonites were investigated using XRD with Rietveld refinement, SEM-EDX and by measuring pH, CEC and EC. Samples extracted from bentonite blocks at 0.1, 1, 4 and 7 cm away from the heating pipe showed various stages of alteration related to the horizontal thermal gradient. Bentonites close to the contact with lower CEC values showed smectite alterations in the form of tetrahedral substitution of Si4+ by Al3+ and some octahedral metal substitutions, probably related to ferric/ferrous iron derived from corrosion of the heater during oxidative boiling, with pyrite dissolution and acidity occurring in some bentonite layers. This alteration was furthermore associated with higher amounts of hematite and minor calcite dissolution. However, as none of the bentonites showed any smectite loss and only displayed stronger alterations at the heater–bentonite contact, the sealants are considered to have remained largely intact.