At room temperature both Fe(III)-exchanged montmorillonite and Fe(III)-hectorite gave similar Mössbauer spectra, each consisting of a single doublet with parameters characteristic of ferric iron. At 77 K the Fe(III)-hectorite gave a spectrum similar to that observed at room temperature, but with the montmorillonite an additional distinct doublet, with relatively large values of both isomer shift and quadrupole splitting, was observed. The Fe(II)-exchanged samples behaved very differently at room temperature and 77 K. At 77 K well-defined doublets were produced; these had quadrupole splittings similar to those shown by the ion and appreciably greater than those observed for Fe(II) in the structural sites in layer-silicates. At room temperature, however, there was no absorption corresponding to ferrous ions in either of the specimens, because the recoil-free fraction was low as a result of the loose association between the ion and the mineral lattice.