Surface passivation in perovskite solar cells can enhance device efficiency, yet incomplete interfacial functionality poses challenges to long-term reliability. Here we present a strategic interfacial engineering approach using sodium heptafluorobutyrate to fully functionalize the perovskite surface. Sodium heptafluorobutyrate acts as an ion shield that tunes the perovskite surface work function and increases the defect formation energy, resulting in an improved interface with the electron transport layer that minimizes recombination and boosts electron extraction under operation. We find that a sodium-heptafluorobutyrate-functionalized perovskite surface promotes a uniform, compact C60 layer that effectively blocks ion diffusion and stabilizes the device stack. This approach allows p–i–n perovskite solar cells to achieve a record power conversion efficiency (PCE) of 27.02% (certified 26.96% with a maximum-power-point-tracking PCE of 26.61%). Devices with an active area of 1 cm2 deliver a PCE of 25.95%. Perovskite solar cells retain 100% of their initial efficiency following 1,200 h of continuous 1-sun illumination at the maximum power point. Devices also demonstrate exceptional thermal stability, retaining 92% of the initial PCE when ageing at 85 °C for 1,800 h and 94% after 200 thermal cycles between –40 °C and +85 °C.