The thermal dehydration of naturally occurring Ca-montmorillonite has been studied by in situ X-ray diffraction at temperatures between 60–120°C. The time-temperature-dependence of the position of the basal (001) reflection reveals that interlayer water loss on isothermal dehydration occurs in two stages. After an initial rapid decrease in interlayer spacing (on shock heating to an isothermal soak temperature) the reaction proceeds towards equilibrium more slowly. Furthermore, the width of the (001) reflection changes with time, reflecting transformation-dependent changes in homogeneity perpendicular to (001) with a maximum in peak width at the point where the rate of the reaction appears to change. This suggests that, as the interlayer spacing collapses, a local change is induced in the structure, affecting the means of movement of the water from the interlayer.