Abstract The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum ( P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application.