Arsenic is the most important hazardous trace element in copper concentrates. In order to separate arsenic from the smelting processes, a pyrometallurgical treatment with additives was developed to deal with high-arsenic copper smelter flue dust high in copper sulfate. Under the optimized conditions of mixing 30 wt% pyrite and roasting at 550 °C under an inert atmosphere for 30 min, more than 92% arsenic was volatilized as a high purity arsenic trioxide by-product while most copper was retained in the calcine to be returned to smelting as a high-copper feed. The high separation of arsenic is due to the transformation from the limited vaporization of arsenate to volatile arsenic trioxide by pyrite at above 460 °C. Two reaction paths of pyrite were identified as follows: one followed the pattern FeS2 → Fe2O3 → FeAsO4 → Fe3O4/Fe2O3 and the other was FeS2 → FeS + S2 (g) → Fe3O4/Fe2O3.