The FEBEX experiment, a full-scale, high-level radioactive waste repository test, ran for ~18 years and hence is the longest-running disposal test to date. The test consisted of a heater emplaced in an envelope of compacted bentonite at the Grimsel test site, Switzerland. The water content of the bentonite was somewhat lower near the heater and increased towards the granite. This phenomenon probably led to gradients in the exchangeable cation population at various locations within the bentonite buffer. The cement (shotcrete) bentonite interface of one block was characterized by a thin (0.1–1.0 mm) reaction zone in which bentonite constituents, carbonates and sulfates occurred. Cation exchange and a slight decrease of the cation exchange capacity were observed near the heater. Oxic corrosion was observed predominantly at the bentonite/steel liner interfaces, pointing towards a role of air entrapped between the liner and heater during emplacement. At the liner surface, intimate intergrowth of bentonite constituents, metal and corrosion products was observed. At the face of the heater, the bentonite blocks were in direct contact with the heater surface without any signs of metal corrosion. Instead, a significant increase in the Mg content was recorded, which is in agreement with previous large-scale disposal tests. The FEBEX experiment proved that the Mg increase and corrosion were independent processes. The increase in Mg may be explained by the formation of trioctahedral domains or the precipitation of neoformed silicates. For the first time, however, brucite was identified as an additional phase that formed at the metal/bentonite interface, pointing towards a special role for Mg mobility in the bentonite barrier.