By developed computer model of the distribution behavior of accessory elements in copper smelting, copper smelting process was simulated. Effect of smelting temperature upon distribution behavior of accessory elements such as Ni, Co, Sn, Pb, Zn, As, Sb and Bi among matte, gaseous phase and fayalite slags or ferrite slags in copper smelting was studied. Ferrite slag is more efficient in removing As and Sb than fayalite slag. The distributions of Sn, Pb, Zn, As, Sb and Bi in gaseous phase increase with increasing smelting temperature significantly.