The photovoltaic performance of perovskite solar cells is severely limited by the innate defects of perovskite films. Metal−organic framework (MOF)-based additives with luxuriant skeleton structures and tailored functional groups show a huge potential to solve these problems. Here, a multilateral passivation strategy is performed by introducing two alkyl-sulfonic acid functionalized MOFs, MIL-88B-1,3-SO 3 H and MIL-88B-1,4-SO 3 H, respectively, obtained from MIL-88B-NH 2 through a postsynthetic process, for coordinating the lead defects and inhibiting nonradiative recombination. The flexible MIL-88B-type frameworks endow both functionalized MOFs with excellent electrical conductivity and preferable carrier transport in the hole-transport materials. Compared with the original MIL-88B-NH 2 and MIL-88B-1,4-SO 3 H, MIL-88B-1,3-SO 3 H exhibits optimal steric hindrance and multiple passivation groups (−NH 2 , −NH−, and −SO 3 H), achieving the champion doped device with an enhanced power conversion efficiency (PCE) of 22.44% and excellent stability, which maintains 92.8% of the original PCE under ambient conditions (40% humidity and 25 °C) for 1200 h.