In planar perovskite solar cells (PSCs), defect-induced recombination at the interface between the perovskite and hole transport layer (HTL) leads to a large potential loss and performance deterioration. Therefore, an effective method for improving interfacial properties is critical to boost the performance and stability of PSCs. Herein, a novel surface engineering technology is reported for passivating the perovskite surface with the polyfluoro organic compound tris(pentafluorophenyl)boron (TPFPB), which can yield large perovskite grains, reduced defect densities, and improved charge transport and phase stability for the perovskite film, and enhanced power conversion efficiency (PCE) and stability for PSCs. Using this strategy, a champion FA0.85MA0.15PbI3 perovskite cell achieves a high PCE of 21.6% as well as significantly improved air and light stabilities. This work demonstrates that TPFPB is a promising material for crystallization control and defect passivation and paves a new path for mitigating defects and further increasing the performance of planar PSCs.