The high-density defect states existing at the grain boundaries and heterojunction interfaces induce nonradiative charge recombination and ion migration processes within perovskite film, which seriously impair the device efficiency and stability. Here, we propose a novel synergistic ion-anchoring passivation (SIP) strategy for high-performance perovskite solar cells, by designing a multifunctional molecule to heal the charged defects via electrostatic interactions. The anion and cation species of the multifunctional molecule are rationally screened via high-throughput DFT simulation and experimental verification, which act as efficient surface passivation agents to heal the lead- and iodine-related defects. As a result, the defect-less perovskite films deliver encouraging device power conversion efficiency >24% with negligible hysteresis. A remarkable open-circuit voltage (Voc) of 1.17 V was obtained with a Voc deficit of 370 mV, featuring the outstanding defect-passivation capability of the SIP strategy. Moreover, the SIP-treated devices show exceptional ambient stability and maintain 70% of the initial efficiency after 150 h of high humidity exposure (relative humidity 70%-80%). Our results highlight the importance of the rational design of passivation agents to realize high-performance perovskite electronics.