A series of laponites and synthetic OH-and fluorinated hectorites prepared from hydrothermal and melting experiments at both industrial and laboratory scale were examined with XRD and FTIR (MIR and NIR) to determine their mineralogical composition and possible compositional heterogeneity. The end materials contained both Li-and Na-bearing phases. The industrial hydrothermal OH-smectites prepared at low temperatures consist of random mixed layer hectorite-stevensite-kerolite with about 40-50% hectorite layers, the remaining being stevensite and kerolite at roughly equal proportions. The FTIR spectra of these smectites contain, besides the main Mg 3 OH stretching/overtone bands at 3695-3690 and 7225-7214 cm −1 , respectively, additional OH overtone bands at ~3716 and 7265 cm −1 (hydrated state). These bands might be linked to Mg 2 LiOH stretching modes. The melt-derived smectites are kerolite-free but still contain stevensite layers, although the preparation methods involved heating in the excess of 1000 • C. In these smectites Li might be partitioned to both octahedral and interlayer sites. Subsequent annealing of the melt-derived Mg-Li smectites caused migration of the exchangeable Li to the vacant octahedral due to the Hofmann-Klemen effect and thus decrease of the layer charge, as was indicated by the νO-D method. Hydrothermal synthesis of Mg-Li smectites at high temperature (400 • C) and pressure (1 kbar), yielded pure hectorite without stevensite or kerolite domains.