The work presents experimental results of an in situ investigation of the OH − absorption in pure and MgO-doped LiNbO3 crystals during reducing (95% Ar + 5% H2) and oxidizing (O2) high-temperature treatments in the temperature range from room temperature to 820 K. The absorption spectra measured in situ at high temperatures in reducing/oxidizing atmospheres have been analyzed. The origin of the changes in optical absorption caused by heating of the crystal is discussed in terms of the OH-bonds orientation change.