Bentonite is to be used as a sealing material for long-term storage of radioactive waste. During permafrost periods the buffer may freeze, causing the following: montmorillonite dehydration, ice formation, and pressure build-up that may fracture the surrounding rock. No previous study has been done on freezing of bentonite in saline water. Using small and wide angle X-ray scattering, the present study aimed to increase understanding of the combined impact of salt and temperature on the hydration (swelling) of Wyoming montmorillonite. The basal spacing of the Na-montmorillonite was very dependent on the water content, while this was not the case for the Ca-montmorillonite (after reaching 19 Å). The basal spacing of the free-swelling Na-montmorillonite (34–280 Å) was estimated successfully using simple calculations. During freezing of Na-montmorillonite in NaCl solution, both ice and hydrohalite formed (at −50 and −100ºC). At starting concentrations ≥1.5 M the basal spacing was not affected by freezing. During freezing of Ca-montmorillonite in CaCl2 solution, ice formed; antarcticite formed only sporadically. The basal spacing of the Ca-montmorillonite at high NaCl concentrations (>1 M) was greater at −50 and −100ºC (18 Å) than at 20ºC (16 Å). The opposite was observed at low concentrations. This change was attributed to small amounts of salts introduced into the montmorillonite interlayer, hence changing the interlayer water properties. The montmorillonite hydration was also temperature dependent; decreasing temperature increased the hydration (as long as no ice was formed) and increasing the temperature decreased the hydration. This was attributed to the temperature impact on the entropy of the hydration reaction. This observation was also reproduced in an experiment up to 90ºC. A small amount of salt in the groundwater was noted to reduce significantly the potential problem of ice formation in bentonite sealings.