In the realm of high–tech industries, Sn has emerged as an indispensable strategic metal. However, the pyrometallurgical refining process of crude Sn is marred by the production of a substantial amount of hazardous solid waste, notably As–Al slag, posing a direct threat to the ecological safety of the production areas. This study delineates a novel process for the removal of As from crude Sn, employing vacuum gasification–directional condensation, corroborated by theoretical calculations and laboratory experimental research. Theoretically, at a system pressure ranging from 1–10 Pa, the initial volatilization temperatures of Sn and As exhibit significant variance. However, the formation of intermetallic compounds can induce Sn volatilization. Experimentally, the condensation temperature for As was predominantly within 331.7–484.7 K. During the vacuum gasification–directional condensation process, the presence of Sn4As3 intermetallic compounds impeded As volatilization. And under optimal conditions, the As content in the Sn product was recorded at 0.0053 %. Inspired from the calculations, a multistage vacuum distillation method was successfully proposed and achieved to remove As from crude tin. Typically, the total material recovery rate is 99.96 %, and the direct rate of Sn is 93.02 %. The total power consumption and emission of this process are better than the corresponding parameters of other treatment processes, which is a promising solution for the cleaning and effective removal of As.