Despite the fact that perovskite solar cells (PSCs) are widely popular due to their superb power conversion efficiency (PCE), their further applications are still restricted by low stability and high-density defects. Especially, the weak binding and ion−electron properties of perovskite crystals make them susceptible to moisture attack under environmental stress. Herein, we report an overall sulfidation strategy via introduction of 1-pentanethiol (PT) into the perovskite film to inhibit bulk defects and stabilize Pb ions. It has been confirmed that the thiol groups in PT can stabilize uncoordinated Pb ions and passivate iodine vacancy defects by forming strong Pb−S bonds, thus reducing nonradiative recombination. Moreover, the favorable passivation process also optimizes the energy-level arrangement, induces better perovskite crystallization, and enhances the charge extraction in the full solar cells. Consequently, the PT-modified inverted device delivers a champion PCE of 22.46%, which is superior to that of the control device (20.21%). More importantly, the PT-modified device retains 91.5% of its initial PCE after storage in air for 1600 h and over 85% of its initial PCE after heating at 85 °C for 800 h. This work provides a new perspective to simultaneously improve the performance and stability of PSCs to satisfy their commercial applications.