Differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) of lithium formate monohydrate (LiHCOO·H2O) were performed in the temperature range 300-700 K. The DSC/TG measurements show that the dehydration process to anhydrous lithium formate (LiHCOO) is complex and occurs in two stages. The data are correlated to the structure and to the arrangement of the molecules in the crystal, including the hydrogen-bonding. Infrared transmittance and Raman spectra of this crystal are reported and commented on.