The adsorption enthalpy and the adsorption isotherm of tetradecylpyridinium bromide (TPB) onto a Na-montmorillonite suspension and the dilution enthalpy of the TPB solution have been determined at 298.15 K. The dilution process is endothermic and the adsorption process is exothermic, For ion exchange adsorption, the interaction between TP+ and the montmorillonite is much stronger than that between Na+ and the montmorillonite because the cumulative adsorption enthalpy increases dramatically with adsorption amount. For molecular adsorption, however, the interaction between TPB and the clay is much weaker.