Samples of natural and synthetic tochilinites and valleriites were investigated by Mössbauer spectroscopy. Synthesis of tochilinite was carried out at different temperatures and Fe/Mg ratio in the initial mixture. The relative amounts of obtained phases as functions of Mg atom relative content in the initial mixture were derived. It was shown that Mg atoms preferred to occupy one of two nonequivalent positions in brucite-like layers when entering the tochilinite structure. Parameters of hyperfine interaction were determined for valleriite and crystal chemical identification of ⁵⁷Fe subspectra was carried out.