The defects in the light-harvesting perovskite absorber layer play a key role in limiting power conversion efficiencies (PCEs) and long-term stability of lead halide perovskite solar cells (PSCs). Although organic ammonium halides have been used for defect passivation in high-performance PSCs, the stability issue is still a challenge. Herein, we develop a novel material of pyridine-carbazole (Py-Cz) to passivate defects via coordination bonding. With this passivation, the photoluminescence intensity of perovskite films was increased. In addition, the formation of under-coordinated Pb2+defects in perovskite films was reduced significantly, enabling high-performance and long-term stable PSCs. Three different sets of PSCs were constructed, namely, without passivation, with phenethylammonium iodide (PEAI) (commonly used for passivation), and with Py-Cz passivation. Remarkably, the PSCs fabricated using the Py-Cz passivation not only achieved PCEs of over 20% but also retained 85% of their initial performances over more than 5000 h. In contrast, the PSCs without or with PEAI passivation degraded quickly during the long-term operational stability test under light illumination. This method opens up a new opportunity to develop highly efficient and operationally stable PSCs.