Recently, introducing pseudo-halide anions to form mixed-anion perovskites has been found to significantly improve the quality of perovskite films, providing an effective strategy for realizing stable and efficient perovskite solar cells. Herein, using density functional theory (DFT) calculations, we explore the possibilities to improve the stability of FAPbI surface and the charge transfer properties of SnO/FAPbI heterostructure by doping pseudo-halide anions. We first study the thermodynamic stability of the perovskite surfaces and find that pseudo-halide-doped FAPbI surfaces are more stable than pristine FAPbI surface. All the SnO/perovskite interfaces form type-II band alignment that can facilitate interfacial electron−hole separation under illumination. Moreover, the bandgap and work function of FAPbI surface can be tuned via using pseudo-halide anions, lowering the conduction band offsets of SnO/perovskite heterostructures. Photo-generated electrons can be easily transferred from perovskites to SnO, which will be favorable for solar cell applications. In addition, pseudo-halide-doped surfaces can also enhance light absorption properties, compared to pristine FAPbI surface. Our DFT calculations indicate that pseudo-halide-doped perovskites can serve as promising photovoltaic materials for optimizing the stability and optoelectronic properties of photoactive layers.