Based on SHS reactive flame spray technology, Al2O3 multiphase ceramics coatings were produced. Chemical copper-plating technology was used to produce the Al-CuO powders of copper cladding, which became individual SHS reactive units respectively. The phenomena and principles of the SHS reactive flame spray of the Al-CuO powders of copper cladding forming Al2O3 multiphase ceramics coatings were investigated. It was found that copper cladding of Al-CuO powders were necessary for the SHS reaction during the spray process. The better the cladding was, the more sufficient the SHS reaction, and the higher the transformation rate was. The Cu and Al2O3 fine molten drops produced by the SHS reaction bumped the substrate and flatted to form layer-shaped Al2O3-based multiphase ceramics coatings. The binding strength between the coating and substrate was as high as 19.8MPa, and the micro-hardness of the coatings was Hv712. The overall properties of the coatings were better than those of the ceramics coatings sprayed by the traditional flame spray.