This work investigated the reaction mechanism of Sb in copper smelting process. The difference of multi-phase distribution of Sb in four typical copper smelting processes was analyzed. A multi-phase equilibrium model of the oxygen-enriched bottom-blow copper smelting process was developed. The impacts of Cu, S, and Sb concentrations in raw materials on Sb distribution in multiphases were researched. This model was also used to investigate the effect of process factors such as copper matte grade, oxygen-enriched concentration, smelting temperature, and oxygen/ore ratio (ratio of oxygen flow rate under standard conditions to concentrate charge rate) on Sb distribution behavior. The results showed that calculation data were in good agreement with the actual production results and literature data. Increasing the Cu content and decreasing the S and Sb contents in the concentrate, increasing the copper matte grade, oxygen/enriched concentration, and oxygen-ore ratio, and at the same time appropriately reducing the smelting temperature are conducive to the targeted enrichment of Sb into the slag. Modeling results can provide theoretical guidance for the clean and efficient treatment of complex resources and the comprehensive recycling of associated elements.