The objective of this research was to carry out a comparative study of the volumetric properties of 2-pyridinemethanol, 3-pyridinemethanol, 2-(hydroxymethyl)piperidine, and 3-(hydroxymethyl)piperidine in aqueous media. The density and excess volumes of mixing as a function of temperature (T=293.15–318.15K) over the entire concentration range are examined for aqueous solutions of 2,3-pyridinemethanols, and the density and partial molar volumes of aqueous solutions are investigated for the corresponding 2,3-(hydroxymethyl)piperidines. The minimum values of the excess molar volumes, v E, are observed, −0.59cm 3 mol − 1 for 2-pyridinemethanol–water solutions and −0.47 for 3-pyridinemethanol–water solutions. These are about 0.61% and 0.49% respectively, of the molar volume. The thermal expansion coefficients α T at 298.15K calculated from the density data, exhibited significant positive deviations, (about 30%) from ideality for 2-pyridinemethanol–water mixtures, and 3-pyridinemethanol–water mixtures. The partial molar volume of 2,3-(hydroxymethyl)piperidines in water at selected temperatures was evaluated by extrapolating the apparent molar volume versus molality plots to m=0. In addition, the partial molar expansivity, E 0 , the isobaric coefficient of thermal expansion, α T , the interaction coefficient, S v , and the Hepler's constant have also been computed. The data are interpreted in terms of the effect of the primary alcohol functional group on the inter/intramolecular and additional hydrophilic interactions between the molecules.