—In some real and up-scale tests using high-level radioactive waste (HLRW), Mg accumulation was observed in smectites at the contact of heated Fe or Cu metal tubes. It is important to understand why Mg accumulated in order to model the long term performance of bentonites in HLRW systems. In some of these tests, an increased number of trioctahedral domains was measured in the smectites using X-ray diffraction (XRD) and infrared spectroscopy (IR). The trioctahedral domains either formed by the dissolution/precipitation of smectites or by the addition of Mg through a solid-state reaction similar to the Hofmann-Klemen effect. The Hofmann-Klemen effect is used in the Greene-Kelly test to distinguish montmorillonites from beidellites. Many studies have been carried out about Li-uptake by smectites, but Mg was rarely taken into account. The present study was, therefore, undertaken to compare the interactions of different bentonites with Li and Mg under various conditions. A significant CEC decrease was found for Li- and Mg-saturated bentonite samples after heating at 250°C under dry conditions. The extent of this CEC reduction depended on the octahedral to tetrahedral charge ratio and was smaller for Mg-saturated samples than Li-saturated samples. This finding proved that it is much more difficult for Mg to enter octahedral vacancies than Li, which probably can be explained by the larger hydration energy and/or slightly larger radius of Mg. The relationship between CEC reduction and the octahedral/tetrahedral charge ratio of both Li- and Mg-saturated samples, however, suggests a similar process. The Mg that can reside at the bottom of the pseudohexagonal holes would not explain this relationship. The important result with respect to understanding HLRW bentonite performance, on the other hand, is that Mg fixation only occurs under dry conditions and that Mg fixation acts as a sink for Mg and, hence, leads Mg to diffuse towards the heated metal surface.