Calorimetry, static technique, and X-ray diffraction (XRD) analysis were employed to study the adsorption of cetyltrimethylammonium bromide (CTAB) and dodecyltrimethylammonium bromide (DTAB) on Fe-montmorillonite and Na-montmorillonite suspensions. The results show that the process of adsorption is exothermic and that the type of clay and the alkyl chain length of surfactant affect the amount of adsorption and the enthalpy of adsorption significantly but that the effect of temperature is very limited in the temperature range studied. The magnitudes of adsorption amount and adsorption enthalpy follow the order Na-montmorillonite > Fe-montmorillonite, CTAB > DTAB. The basal spacings determined by X-ray powder diffraction indicate that the CTAB adsorbed between the clay interlayers in a bilayer arrangement, while the DTAB formed bilayers or monolayers at saturation adsorption between the Na-montmorillonite and Fe-montmorillonite interlayers, respectively. The adsorption mechanism is also discussed on the basis of the experimental data.