Defect passivation has been recognized as an effective strategy to improve efficiency and stability of perovskite solar cells (PSCs). In this work, in-depth theoretical calculations and experimental characterizations reveal the dual-site synergistic passivation of 1H-benzimidazole (BIZ), and the conjugated structure of the benzene ring tends to increase the interaction between BIZ and perovskite. High-quality perovskite films are thus achieved, with increased grain size, reduced defect density, and suppressed ion migration. Simultaneously, the reduced work function and optimized band alignment promote carrier transport, reducing nonradiative recombination, and loss of open-circuit voltages, as well as fill factor. Consequently, the target PSC devices achieve a champion power conversion efficiency (PCE) of 24.59%, and 20.49% for perovskite solar module (a designated area of 27.5 cm(2)). The unencapsulated PSC maintains 91.49% of original PCE after storing in air with an average relative humidity of 40% for 2400 h. Moreover, the device exhibits remarkable the long-term operational stability, maintaining 90.47% of initial PCE after continuously operating at the maximum power point for 1000 h. This study not only provides insights into the synergistic passivation of BIZ but also provides a strategy for the application of BIZ derivatives in the photovoltaic field.