Hydrothermal deposition of antimony selenosulfide (Sb 2 (S,Se 3 )) has enabled solar cell applications to surpass the 10% efficiency threshold. This deposition process involves the reaction of three precursor materials: Sb, S, and Se. However, this process generates an unfavourable gradient of Se and S anions in the Sb 2 (S,Se) 3 film, which limits further efficiency improvements. Herein, we demonstrate how NH 4 F can be used as an additive to regulate the band gradient of the Sb 2 (S,Se) 3 and modify the surface of the CdS electron-transporting layer. On the one hand, NH 4 F inhibits the decomposition of Na 2 S 2 O 3 and selenourea, which optimizes the deposition process and allows for adjustment of the Se/S ratio and their distribution in the Sb 2 (S,Se) 3 film. On the other hand, hydrolysis of NH 4 F induces dissolution and redeposition of CdS, thereby effectively improving the morphology and crystallinity of the CdS substrate. Finally, the dual effect of NH 4 F enables improved surface morphology and energy alignment of the Sb 2 (S,Se) 3 film, thus yielding a maximum efficiency of 10.28%, a 12% improvement over the control device. This study demonstrates an effective strategy for simultaneously modifying a sulfide-based substrate and regulating the element distribution during the deposition of a metal chalcogenide film for optoelectronic device applications.