Perovskite solar cells have emerged as a potential competitor to the silicon photovoltaic technology. The most representative perovskite cells employ SnO2 and spiro‐OMeTAD as the charge‐transport materials. Despite their high efficiencies, perovskite cells with such a configuration show unsatisfactory lifespan, normally attributed to the instability of perovskites and spiro‐OMeTAD. Limited attention was paid to the influence of SnO2, an inorganic material, on device stability. Here we show that improving SnO2 with a redox interfacial modifier, cobalt hexammine sulfamate, simultaneously enhances the power‐conversion efficiency (PCE) and stability of the perovskite solar cells. Redox reactions between the bivalent cobalt complexes and oxygen lead to the formation of a graded distribution of trivalent and bivalent cobalt complexes across the surface and bulk regions of the SnO2. The trivalent cobalt complex at the top surface of SnO2 raises the concentration of (SO3NH2)‐ which passivates uncoordinated Pb2+ and relieves tensile stress, facilitating the formation of perovskite with improved crystallinity. Our approach enables perovskite cells with PCEs of up to 24.91%. The devices retained 93.8% of their initial PCEs after 1000 hours of continuous operation under maximum power point tracking. These findings showcase the potential of cobalt complexes as redox interfacial modifiers for high‐performance perovskite photovoltaics.