Abstract: Multivariate analysis of variance and discriminant analysis were used to establish the crystal chemistry of several Al-rich smectites. The statistical analyses were carded out on 78 samples taken from the literature which were classified on the basis of their physicochemical properties. A strong discrimination exists between beidellites and montmorillonites, ‘non-ideal’ montmorillonites and ‘ideal’ montmorillonites, and Wyoming-type and Cheto-type montmorillonites. Of the Cheto-type montmorillonites, the Tatatilla-type samples are strongly discriminated, whereas the distinction between Chambers- and Otay-types is not strong. AlIV, AlVI, Fe, Mg, and Ca are generally important discriminating variables, whereas the tetrahedral portion of the layer charge, commonly used as a discriminating factor among these minerals, is only moderately significant.