Surface-covered nanometer-sized CuO/Al2O3, CuO-ZnO/Al2O3, and CuO/ZnO catalysts were prepared by phase transfer with carboxylate. The surface-covered structure was studied using XPS, XRD, TEM, and high-resolution electron microscope. The results indicated that amorphous CuO and ZnO were dispersed on the surface of nanometer-sized Al2O3 particles in catalysts CuO-ZnO/Al2O3 and CuO/Al2O3, respectively. The thickness of its surface layer is about several angstroms. No spinel structure was found in the catalyst. The particle size of the surface-covered CuO/Al2O3 catalyst was about 2-3 nm. Al2O3 in the catalyst was amorphous. Surface-covered material CuO in the catalyst with low CuO content was also armophous. A large amount of copper carboxylate resulted in crystalline CuO and Cu2O. The protective ability of carboxylate to sol particles differs from the metal element of carboxylate.