The adsorption isotherms and adsorption enthalpies of dodecyltrimethylammonium bromide (DDTMAB) on Na- and Al-montmorillonite were determined in the pH range 2-12. The basal spacings of the clays were also studied by X-ray diffraction. Interactions of DDTMAB with the two montmorillonites predominate mostly through cation exchange in the pH range studied. In the case of Na-montmorillonite, the amount of adsorption increases with pH, but adsorption enthalpy decreases with pH. For Al-montmorillonite, adsorption enthalpy exhibits nonnonotonic variation with pH, although the amount of adsorption increases with pH monotonously. The adsorption enthalpies of DDTMAB on the clays are negative. The adsorbed DDTMAB molecules in clay interlayers present a bilayer arrangement at saturation.