Five Fe–bearing dioctahedral smectites (three nontronites and two Fe-rich smectites) were purified using a variety of physical and chemical procedures. The structural formulae indicate one nontronite and one Fe-rich smectite to be montmorillonitic, whereas the other three smectites are beidellitic. Mössbauer spectra showed Fe to be exclusively trivalent and were fitted with three doublets, two of which had quadrupole splittings characteristic of Fe3+ in octahedral coordination, whereas the third had a distinctly lower quadrupole splitting. Although the position of the Si–O stretching band in the infrared spectra could reflect tetrahedral Fe3+, the lack of distinctive features prevented a definitive attribution of this component to tetrahedral Fe3+. The 18O/16O data suggest that fractionation of nontronite-water at ambient temperatures (1000 lnα = 23 ± 2‰) is lower than that of Fe-rich smectite (1000 lnα = 27 ± 2‰). The estimated formation temperatures of the samples are below 70°C.