Thermodynamic analysis of simultaneous and sequential adsorption of crystal violet (CV) and 2-naphthol adsorption on montmorillonite has been conducted, and the changes of microstructure of the clay after adsorption were investigated using X-ray diffraction (XRD). The basal spacing and structural order of CV and 2-naphthol adsorbed montmorillonites varied with different CV loadings. In principle, larger basal spacing was resulted from a higher loading of CV in montmorillonites. The excellent structural order of the resultant hybrids is achieved in samples with 0.50-0.75 CEC (cation exchange capacity) loadings of CV. The effects of temperature and ionic strength on the adsorption of CV and 2-naphthol on montmorillonite were also investigated. The Freundlich isotherm model was applied for curve-fitting of the equilibrium isotherm data. The resulting thermodynamics parameters suggested that the sorption process was a spontaneous exothermic process in the case of low CV concentrations. The negative values of Gibbs free energy in all of the adsorption processes indicated that these processes are spontaneous processes. With the increase of CV concentration, the sequential adsorption of 2-naphthol onto montmorillonite proved to be an endothermic process.