Diffuse reflectance spectra in the near-infrared region are presented for Li-saturated smectites heated up to 200°C. The smectites included three montmorillonites, an Fe-beidellite and a ferruginous smectite. Unheated samples showed a complex band near 7060 cm−1 assigned to the first overtone of the OH-stretching mode of structural hydroxyl groups and bound H2O. The OH combination bands appeared in the 4600–4300 cm−1 region. Spectra of heated montmorillonites showed an upward shift and splitting of the OH-overtone band into two components near 7170 and 7110 cm−1. The presence of a band near 7170 cm−1, assigned to the overtone of the AlMgLiOH-stretching vibration, implied that local trioctahedral domains were created upon Li(I) fixation in the previously vacant octahedral positions of montmorillonites. The OH combination bands were shifted to higher frequencies and a new band appeared near 4472 cm−1 in the spectra of montmorillonites heated to temperatures in excess of 130°C. No features indicating Li(I) in the structure of Fe-beidellite or ferruginous smectite were observed in the NIR spectra.