The stability and efficiency of inorganic perovskite solar cells (PSCs) remain limited owing to the presence of interfacial and bulk-related defects. To address this issue, a multifunctional defect-passivating interlayer can be introduced. In this study, 1,1 '-bis(3-sulfonatopropyl)-viologen (BSP-Vi) was synthesized for depositing a multifunctional interlayer between a TiO2 electron transport layer (ETL) and CsPbI3 perovskite absorber. The sulfonate group in BSP-Vi effectively interacts with both oxygen vacancies on the TiO2 surface and undercoordinated Pb2+ species in the perovskite, leading to substantial defect passivation in both the ETL and perovskite absorber. BSP-Vi induces a favorable shift in interfacial energy levels and facilitates the formation of a perovskite film with improved crystallinity and reduced defect density. Consequently, the optimized PSC incorporating 0.2 wt% BSP-Vi achieves a power conversion efficiency (PCE) of 16.93%, representing a marked increase from that of the control (PCE = 16.08%). The maximum power point tracking test demonstrates that the PSC with BSP-Vi-treated interlayer maintained 95% of the initial performance after 160 h of continuous operation. This study highlights the potential of introducing sulfonate-group-based materials at the ETL/perovskite interface as a promising route to simultaneously passivate defects in and enhance the efficiency and stability of inorganic perovskite photovoltaic devices.