The benefits of excess PbI2 on perovskite crystal nucleation and growth are countered by the photoinstability of interfacial PbI2 in perovskite solar cells (PSCs). Here we report a simple chemical polishing strategy to rip PbI2 crystals off the perovskite surface to decouple these two opposing effects. The chemical polishing results in a favorable perovskite surface exhibiting enhanced luminescence, prolonged carrier lifetimes, suppressed ion migration, and better energy level alignment. These desired benefits translate into increased photovoltages and fill factors, leading to high-performance mesostructured formamidinium lead iodide-based PSCs with a champion efficiency of 24.50%. As the interfacial ion migration paths and photodegradation triggers, dominated by PbI2 crystals, were eliminated, the hysteresis of the PSCs was suppressed and the device stability under illumination or humidity stress was significantly improved. Moreover, this new surface polishing strategy can be universally applicable to other typical perovskite compositions.