We investigate the effects of redox reaction on preparation of high purity α-alumina from selectively ground aluminum dross. Preparation procedure of the α-alumina from the aluminum dross has four steps: i) selective crushing and grinding, ii) leaching process, iii) redox reaction, and iv) precipitation reaction under controlled pH. Aluminum dross supplied from a smelter was ground to separate metallic aluminum. After the separation, the recovered particles were treated with hydrochloric acid(HCl) to leach aluminum as aluminum chloride solution. Then, the aluminum chloride solution was applied to a redox reaction with hydrogen peroxide(H2O2). The pH value of the solution was controlled by addition of ammonia to obtain aluminum hydroxide and to remove other impurities. Then, the obtained aluminum hydroxide was dried at 60oC and heat-treated at 1300oC to form α-alumina. Aluminum dross was found to contain a complex mixture of aluminum metal, aluminum oxide, aluminum nitride, and spinel compounds. Regardless of introduction of the redox reaction, both of the sintered products are composed mainly of α-alumina. There were fewer impurities in the solution subject to the redox reaction than there were in the solution that was not subject to the redox reaction. The impurities were precipitated by pH control with ammonia solution, and then removed. We can obtain aluminum hydroxide with high purity through control of pH after the redox reaction. Thus, pH control brings a synthesis of α-alumina with fewer impurities after the redox reaction. Consequently, high purity α-alumina from aluminum dross can be fabricated through the process by redox reaction.