Because of the compatibility with tandem devices and the ability to be manufactured at low temperatures, inverted perovskite solar cells have generated far-ranging interest for potential commercial applications. However, their efficiency remains inadequate owing to various traps in the perovskite film and the restricted hole blocking ability of the electron transport layer. Thus, in this work, a wide-bandgap n-type semiconductor, 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-phenylpyrimidine (B4PyPPM), to modify a perovskite film via an anti-solvent method is introduced. The nitrogen sites of pyrimidine and pyridine rings in B4PyPPM exhibit strong interactions with the undercoordinated lead ions in the perovskite material. These interactions can reduce the trap state densities and inhibit nonradiative recombination of the perovskite bulk. Moreover, B4PyPPM can partially aggregate on the perovskite surface, leading to an improvement in the hole-blocking ability at its interface. This modification can also increase the built-in potential and upshift the Fermi level of the modified perovskite film, promoting electron extraction to the electron transport layer. The champion device achieves a high efficiency of 23.51%. Meantime, the sealed device retains approximate to 80% of its initial performance under a maximum power point tracking for nearly 2400 h, demonstrating an excellent operational stability.