Carbon residue in aluminum electrolytic cell is a kind of hazardous waste produced during the smelting and production process of the aluminum industry. The accumulation of a large amount of carbon residue wastes electrolyte resources, as well as causing air, soil and water pollution. In this experiment, carbon residue was used as raw material and Na2CO3 was used as additive to study the feasibility and process of recovering carbon powder and cryolite by the roasting-water leaching process of carbon residue. The carbon residue with a mass ratio of 2.5:1 was mixed with Na2CO3, then placed in a crucible-resistance furnace, and baked at 950°C for 2h. The test results show that the alumina, cryolite and sub-cryolite in the carbon residue are consumed by Na2CO3, and the mixture after roasting is composed of C, Na2CO3, NaF, and NaAlO2. After roasting, the mixture is leached for 1 hour when the pH of 14 and leaching temperature of 25°C. The purity of the recovered carbon powder after solid-liquid separation can reach 89%. The carbonation method is used to recover F－ in the leachate to obtain powdered cryolite with qualified main components. Properly increasing the roasting temperature and extending the holding time can improve the separation efficiency of carbon and electrolyte. Research on economical and effective carbon residue treatment methods can not only solve the environmental pollution caused by carbon residue, but also have a profound impact on the sustainable development of society.