Reducing heterointerface nonradiative recombination is a key challenge for realizing highly efficient perovskite solar cells (PSCs). Motivated by this, a facile strategy is developed via interfacial energetics reversal to functionalize perovskite heterointerface. A surfactant molecule, trichloro[3-(pentafluorophenyl)propyl]silane (TPFS) reverses perovskite surface energetics from intrinsic n-type to p-type, evidently demonstrated by ultraviolet and inverse photoelectron spectroscopies. The reconstructed perovskite surface energetics match well with the upper deposited hole transport layer, realizing an exquisite energy level alignment for accelerating hole extraction across the heterointerface. Meanwhile, TPFS further diminishes surface defect density. As a result, this cooperative strategy leads to greatly minimized nonradiative recombination. PSCs achieve an impressive power conversion efficiency of 25.9% with excellent reproducibility, and a nonradiative recombination-induced qVoc loss of only 57 meV, which is the smallest reported to date in n-i-p structured PSCs.