FT infrared spectrometer was used to obtain a series of infrared spectra at various temperatures of pentaerythritol(PE)、pentaglycerine(PG)、neopentylglycol(NPG) and their binary mixtures.The shifts of -OH absorption peak reveal the solid solid phase transition mechanisms and the connection of wave number shifts with temperature and enthalpies of phase transition.The solid solid phase transitions of the three polyols and their binary mixtures are known to transform from a low symmetric layered crystal structure to a highly symmetric face centered cubic structure.Experimental results support a mechanism which involves reversible breaking of nearest neighbor hydrogen resonance bonds in the molecular crystals at the transformation temperature.Infrared spectra show reversible increase in the wave number of the absorption peak of -OH groups with reversible breaking of the hydrogen bonds.This is in agreement with the experimental results of X ray diffraction and thermal analysis.