Based on the properties of antimony (Sb) and arsenic (As), a method was proposed to enhance gold recovery during iron matte smelting. The impact of Sb and As on gold enhancement capture was investigated using an exclusion method. The results demonstrated that both Sb and As significantly improved the gold recovery rate. As the Sb or As content increased, the gold recovery rate increased. The enhancement effect of Sb was better than that of As, and the optimal results were achieved through the synergistic effects of Sb and As. Under optimized conditions, the gold recovery rate reached 97.12%, whereas the gold content in the slag decreased to 1.70 g/t. Sb captured and aggregated free gold as an Au-Sb alloy, whereas As-Fe alloy also captured free gold. The growth of the gold-captured phase size enhanced the settling velocity, thereby promoting gold recovery.