As a fundamental study to develop a new process for eliminating detrimental antimony, recovering precious metals from the antimony-rich matte produced from the copper concentrate, and treating the occasionally generated speiss in nonferrous smelting processes, the phase relations in the Cu-Fe-S-Sb system saturated with carbon and the distribution of some minor elements between the phases in the miscibility gap, where three equilibrated phases of iron-rich alloy, copper-rich alloy and matte coexist, were investigated at 1200°C by using a quenching method. The experimental results were compared with the results for the Cu-Fe-S-As-C system and discussed on the basis of activity coefficient of antimony in the matte phase at different matte grades. By utilizing the obtained data, material balance calculations concerning to the treatment of antimony-rich matte produced in copper smelting by adding the pig-iron was elaborated and also laboratory scale experiments using industrial matte were carried to corroborate the calculations. By using the phase separation, the cleaning of complex matte, the recovery of valuable copper, silver and gold into the copper-rich alloy and matte phases as well as the elimination of iron and an acceptable amount of antimony into the iron-rich alloy phase for discarding as a harmless and smaller deposit might be feasible.