Interfacial modification is a key strategy for improving the performance of perovskite photovoltaic devices. However, most commonly, improvements in device performance through surface treatments of the perovskite active layer are attributed to defect passivation. At the same time, such treatments may also lead to the formation of a dipole at the surface of the perovskite active layer. In this work, we demonstrate that treatments that modify the surface stoichiometry of CsPbI₃ perovskites can lead to effective defect passivation, yet result in the formation of surface dipoles of opposing directions that modulate the work function of CsPbI₃ over a range of more than 2 eV. Such dipoles influence the built-in potential of the devices and the efficiency of interfacial charge transfer in CsPbI₃ solar cells, resulting in power conversion efficiencies that increase from below 10% to ∼20% depending on the surface dipole. The surface stoichiometry also has a strong influence on device stability, where initially high-performing devices are found to be prone to a more rapid degradation. These results highlight that the formation of surface dipoles plays a crucial role in impacting the performance and stability of CsPbI₃ solar cells, making the choice of device architecture particularly important.