Realizing efficient and stable perovskite photovoltaic devices remains a key challenge for further development in this field. Surface defects, especially those caused by unbound Pb, are often linked to the performance of these devices. This study demonstrates that NdF3 deposited on the surface of perovskite films effectively passivates unbound lead, thereby improving film quality. The resulting device achieved an power conversion efficiency (PCE) of 22.88% and exhibited good stability. Even after being stored in air for 1400 h, the device maintained its initial PCE of 87.5%. Additionally, after aging at 120 °C for 400 h in a nitrogen atmosphere, the device still retained 90% of its initial PCE. Furthermore, the device maintains 52% of its initial PCE after 1000 h of continuous light soaking.