The1H-NMR spectra of butane-1,2-diol (BD-1,2)-water mixtures as function of concentration were recorded at 298 K and the spectral parameters, Δ δ (BD-1,2-H2O) were evaluated. The surface tensions (σ12) were measured at 298.15 K. From literature values of density (d12) viscosity (η12), dielectric permittivity (ε12) and the measured surface tensions the molar volumes (V12) and their deviations from “ideality”, at 298.15 K, were calculated. Further on the temperature coefficients of dielectric permittivity, α12' were evaluated. These structural parameters as functions of concentration suggest the formation of the “complexes” (sub-units) of the BD-1,2 · 2H2O, BD-1,2 · 4H2O and 2BD-1,2 · H2O types.