High-performance wide-bandgap perovskite solar cells (PSCs) are essential for surpassing theoretical efficiency limits through tandem configurations. However, their performance is often bottlenecked by severe nonradiative recombination at buried interfaces. In p–i–n architectures, the NiOx/perovskite interface is particularly critical, as it dictates both charge extraction and film crystallinity. Herein, we introduce a quinoxaline-based donor–acceptor organic interlayer tailored for the NiOx/perovskite interface. This interlayer effectively passivates interfacial defects, suppresses recombination, and enhances perovskite film quality. Furthermore, its high dipole moment augments the built-in potential, providing a stronger driving force for charge separation. Consequently, the PCE increased from 17.5% to 20.0%, with robust operational stability maintained for over 500h under ambient conditions