The effect of heating on the water sorption capacity of a La-saturated montmorillonite, La-Mt, has been investigated. Sodium and Li as exchangeable ions have also been included for comparative purposes. XPS of La-Mt shows no migration of La(III) from interlamellar positions to octahedral sites on heating at 300°C. The water adsorbed as a multilayer on the external surface of the montmorillonite has been subtracted from the total sorbed water. Although the c-spacing of La-Mt corresponds to a two-layer hydrate, in the relative humidity range from 30 to 70%, the interlamellar water amounts to only 70% of the value for a complete monolayer. Heating at 300°C for 24 h has no influence on the uptake of molecular water between the structural layers of the La-Mt. The average numbers of water molecules per exchangeable ion sorbed into the interlamellar spacing up to 50% r.h. are: 5(Na-Mt), 3(Li-Mt) and 13(La-Mt).