In order to examine the mixing properties of glycerol-water and diglycerol-water solutions, these solutions were measured using attenuated total reflection infrared spectroscopy. The absorbance spectra corrected for 1 mu m thickness were subtracted by pure polyols for obtaining water spectra, and by pure water for polyol spectra. Both asymmetric and symmetric CH2 stretching vibration bands (around 2940, 2885 cm(-1)) shifted about 10 cm(-1) to lower wavenumber side (redshifts) with increasing polyol concentrations, especially at higher concentrations. Redshifts of C-O-H rocking bands (around 1335 cm(-1)) with increasing polyol concentrations are slightly larger for diglycerol-water (10 > 6 cm(-1)) than glycerol-water solutions. C-O stretching bands of CHOH groups (1125 and 1112 cm(-1)) shift slightly but in opposite sides for glycerol and diglycerol at highest polyol concentrations (90-100 wt%). These shifts of CH2 stretching, COH rocking, and CO stretching of CHOH at higher polyol concentrations suggest interactions of outer CH2 with inner CHOH groups of surrounding polyols. The normalized band area changes with polyol concentrations could be fitted by quadratic polynomials possibly due to mixtures of different interactions between water-water, polyol-water, and polyol-polyol molecules. The OH stretching band for diglycerol 90 wt% shows three humps indicating at least three OH components: long, medium, and short H bond water molecules. Short H bond water molecules are the major component possibly between inner CHOH and outer side CH2OH groups, while the long H component might loosely bind to outer CH2OH groups.