Controlling the perovskite morphology and defects at the buried perovskite-substrate interface is challenging for inverted perovskite solar cells. In this work, we report an amphiphilic molecular hole transporter, (2-(4-(bis(4-methoxyphenyl)amino)phenyl)-1-cyanovinyl)phosphonic acid, that features a multifunctional cyanovinyl phosphonic acid group and forms a superwetting underlayer for perovskite deposition, which enables high-quality perovskite films with minimized defects at the buried interface. The resulting perovskite film has a photoluminescence quantum yield of 17% and a Shockley-Read-Hall lifetime of nearly 7 microseconds and achieved a certified power conversion efficiency (PCE) of 25.4% with an open-circuit voltage of 1.21 volts and a fill factor of 84.7%. In addition, 1–square centimeter cells and 10–square centimeter minimodules show PCEs of 23.4 and 22.0%, respectively. Encapsulated modules exhibited high stability under both operational and damp heat test conditions.