Copper smelting slag and gypsum residue are by-products in copper making processes, and both contain valuable elements, such as copper, sulfur, etc. However, there is more than 0.25 wt% Cu in the smelting slag, which cannot be recovered with present technologies. A sulfidation process, which used the gypsum residue as the sulfur resource, was proposed and studied in treating copper smelting slag. Obtained results showed: 1) CaSO4 transformed to CaS under reductive decomposing conditions, and reactions between CaS and slag components occurred spontaneously during the slag cooling process; 2) the Fe/SiO(2 )mass ratio of the slag, the CaS excess coefficient (alpha), and the cooling rate (v) had an influence on the terminal phase composition, sulfide particle size, etc.; 3) under optimized conditions (Fe/SiO2=1.0: alpha=5, v = 1.00C/min; Fe/SiO2=1.3: alpha=4, v = 0.25C/min; Fe/ SiO2=1.8: alpha=5, v = 0.25C/min), the Cu contents in non-sulfide phases were lower than 0.08 wt%, and the mean particle size of sulfides were 37-40 mu m, which were feasible for flotation recoveries. TCLP (Toxicity Characteristic Leaching Procedure) tests indicated that the co-treatment process improved the stability of these starting materials. Based on samples characterization and thermodynamic analysis, a corresponding reaction mechanism was proposed.