Aluminum ash is a kind of industrial solid waste. Original aluminum ash (OAA) can be prepared into original aluminum ash spray powder (OAASP) through hydrolysis treatment, and the original aluminum ash coating (OAAC) can be prepared on the surface of the substrate by plasma spraying. In order to optimize the performance of the OAAC, the OAASP was screened to select the appropriate particle size to improve the flowability of the powder. Then, the influence of the alumina content on coating performance was studied through comparative experiments. The micro morphology of the coating was analyzed, and the performance parameters of the coating were tested. The results show that the spray powder with a particle size of 120–150 mesh accounts for the largest proportion of OAASP, and its flowability is better than that of unsieved OAASP, which is suitable for coating preparation. The performance of the coating can be improved by adding high-purity alumina. When the Al2O3 addition is 50%, the porosity of the coating is 0.131%, the adhesive strength is 17.12 MPa, the microhardness is 713.36 HV, and the abrasion rate 10.31 mg/min. Compared with the coating without Al2O3, the porosity is decreased by 19.63%, the adhesive strength is increased by 5.35%, the microhardness is increased by 17.61%, and the abrasion rate is decreased by 19.83%. There are regions with different brightness on the surface of the coating with Al2O3. After semiquantitative analysis, the main phase in the bright region is Al2O3, and the main phases in the dark and gray regions are Al2O3, SiO2, and Fe3O4. The performance of the OAAC can be optimized by improving the flowability of the sprayed powder and increasing the alumina content.