The experiments were performed in solution for the synergistic adsorption of dodecylbenzene sulfonate and copper ions onto kaolinite surfaces. The results showed that the former enhances the binding constant of copper ions onto kaolinite surfaces, but copper ions deduce the binding constant of dodecylbenzene sulfonate onto kaolinite surfaces. At the same time, they depress the proton release or absorb each other during their adsorption on kaolinite surfaces.