Arsenic-containing multi-metallic materials, are typical hazardous wastes generated in the process of tin recovery from zinc smelting leach slag, exhibit low resource utilization and pose a significant risk of environmental pollution. This research proposed a vacuum reduction roasting technique utilizing anthracite as the reducing agent to remove arsenic and reclaim tin from such materials, characterized by high arsenic levels (8∼wt%) and the presence of several valuable metals. The results indicated that the arsenate in these materials was transformed into As2O3, which has better volatility, while SnO2 was converted to SnO and Sn. Moreover, under the optimal conditions of a roasting temperature of 750 °C, 10 % anthracite, and a roasting duration of 3 h, the arsenic removal efficiency reached 96.97 %, and the tin recovery rate was 84.48 %. Consequently, the arsenic concentration decreased to 0.53 %, and the tin concentration in the roasted product increased from 17.70 % to 31.41 %. The final product contained phases of arsenic and tin, including Sn, SnO2, and FeAs. Meanwhile, this study provides a promising solution for the green and efficient separation of tin and arsenic in typical arsenic-containing multi-metallic materials.