To improve tribological performance of inorganic aluminum phosphate composite coating at high temperature，the hybrid materials of multi-walled carbon nanotubescovered by aluminum oxide was prepared and added to above coatings. The properties andstructure of the hybrid materials were determined by X-ray diffraction analysis（XRD），Fourier transform infrared spectroscopy（FT-IR），Raman spectroscopy，thermogravimetry analysis（TG）， and scanning electron microscopy（SEM）. And the effect of filler content on mechanical properties and wear resistance of the composite coatings were studied. All the results showedthat nano-Al₂O₃ was successfully grafted on the surface of multi-walled carbon nanotubes（MWCNTs）. The surface-modified MWCNTs’ oxidation temperature could be increased by over 100 ℃，and was dispersed more easily. The hardness and bonding of the coatings showeda tendency of increasing and then dropping with the increasing Al₂O₃-MWCNTs content，when the Al₂O₃-MWCNTs was 0. 4% of the total coating component，the hardness could be increased to nearly twice as much，and its adhesion raised to nearly 2. 6 times. The results ofthe friction and wear coupling test at high temperature of 600 ℃ demonstrated that when thecontent of Al₂O₃-MWCNTs was 0. 4%，the friction coefficient of the coating reduced to 0. 659， and the wear rate reached the lowest value of 2. 73×10^-4 mm³/（ N·m）. Which indicated that the introduction of Al₂O₃-MWCNTs hybrid materials enhanced the tribological performance of inorganic phosphate.