The distribution of gold colloids in kaolinite and the interaction between gold and kaolinite surface were investigated by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). There is strong interaction between the gold particles and the edge surfaces of kaolinite,in low pH solution,the edge surface of kaolinite is positively charged and electrostatic attractive force between colloide gold particles and the positive edge surface of kaolinite would facilitate the adsorption of colloidal gold particles onto the suface. TEM observation shows that the aggregate morphology of gold particles was dominated by particle-particle interaction and gold particles were adsorbed on the edge surface of kaolinite crystals, resulting from the electrostatic attractive force between colloidal gold particles and the positive surfaces of kaolinite. XPS data show that in Au4f electron spectra there are four energy peaks related to gold, 83.8 eV, 85.7 eV, 87.5 eV, and 89.4 eV, respectively, which suggests that in chemical states there are metallic gold and Au bonded to O, similar to the form of Au2O3, and composite Au2O3 is formed between the edge surface of kaolinite and colloidal gold surface.