Excess molar enthalpies and excess molar volumes of binary mixtures containing ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, or poly(ethylene glycol)s (PEG200, PEG300, PEG400, and PEG600) + benzyl alcohol were determined at 308.15 K and at atmospheric pressure using a flow microcalorimeter and a digital density meter. Results were fitted to the Redlich-Kister polynomial to estimate the binary interaction parameters. The results are interpreted in terms of molecular interactions between the components.