Chlorites from Cambrian basaltic vesicular lavas, characterized by relatively high Xc (0.81–0.98), gave temperatures of formation of 285 to 350°C (Cathelineau’s empirical geothermometer). Both the Xc and temperature calculations gave results which were too high for the diagenetic conditions indicated by the interbedded shale mineralogy. The HRTEM and XRD studies indicate the absence of smectite layers in these chlorites; i.e. according to lattice images, the actual value of Xc is 1. The chlorite composition in these basaltic lavas must, therefore, be explained in relation to their whole-rock geochemistry, with which a good correlation has been found. The basaltic lavas are characterized by relatively high FeO/MgO ratios (3.2831.66) and must be considered as an Fe-rich system, with similar chemical behaviour to pelitic rocks. In these cases, direct chlorite formation, without a previous smectite precursor, is a normal occurrence and the Xc calculation and empirical geothermometric calculations are inadequate.