This paper chiefly deals with the properties of polyols - a kind of energy storage material, by IR spectra. A series of infrared spectra at various temperatures were obtained for pentaerythritol (PE), pentaglycerine (PG), neopentylglycol (NPG) and their mixture NPG/PG. The experimental results (the shifts of -OH absorption band in IR spectral support the solid-solid phase transition mechanism, which involves the reversible breaking of nearest-neighbor hydrogen bonds in the molecular crystals at transformation temperature. The correlation between the wave number shifts and the temperatures of phase transition is proposed in this paper. Finally, by means of infrared spectroscopy experiments, it is shown that aging has a great influence on the thermal properties of polyol mixtures.