The relationships between the composition and the crystallization temperature of chlorites and illites have been investigated in different geothermal fields and in particular the Los Azufres system in Mexico, considered to be a natural analogue to experimental laboratories, as the main changes in physical and chemical conditions and mineralogy are related to progressively increasing temperature with depth. Temperature was estimated from combined geothermometric approaches, and especially from fluid inclusion studies on quartz coexisting with clays. The Al(IV) content in the tetrahedral site of chlorites, and the K content and total interlayer occupancy of illites increase with temperature. These chemical changes are mainly related to the marked decrease in the molar fraction of the Si(IV)-rich end-members (kaolinite for chlorites, and pyrophyllite for illites) which become negligible at ∼300°C. Other chemical changes, such as the variation in Fe and Mg contents, are partly influenced by temperature, but are strongly dependent on the geological environment, and consequently on the solution composition. The empirical relationships between chemical variables and temperature were calibrated from 150–300°C, but extrapolations at lower and higher temperatures seem possible for chlorites. Such geothermometers provide tools for estimating the crystallization temperature of the clays, and are important for the study of diagenetic, hydrothermal and low-T metamorphic processes.