Pillared montmorillonite was used as an adsorbent for binary mixtures of hydrocarbons and alcohols (benzene/n-heptane; ethanol/cyclohexane; ethanol/toluene; propanol/toluene). The adsorbent was prepared from the Na-form of a bentonite from Milos by reaction with polyhydroxoaluminium solutions. The adsorption behaviour of the pillared montmorillonite was characterized by the adsorption excess isotherms and the heats of immersion. Sorption capacities and wetting properties differed significantly from those of the Na-montmorillonite. Benzene was adsorbed preferentially from mixtures with n-heptane. Ethanol and propanol were also preferentially adsorbed from mixtures with cyclohexane and toluene but the curves showed azeotropic points at molar fractions of alcohols of 0.7-0.9. The calorimetric data revealed the partially hydrophobic character of the pillared montmorillonite. The heat of wetting of benzene or toluene on the pillared samples was distinctly higher than that of ethanol whereas ethanol gave the highest wetting enthalpies on Na-montmorillonite.