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Interfacial instability—originating from defects, ion migration, and uncontrolled crystallization—remains a critical challenge for perovskite solar cells (PSCs). Electron‐withdrawing materials (EWMs) have emerged as promising candidates for interface engineering due to their distinctive coordination capability and favorable charge extraction properties. This review outlines the fundamental characteristics of EWMs and the underlying mechanisms by which they enhance photovoltaic performance and device stability. Recent advances in incorporating such materials across key interface layers are systematically summarized, offering mechanistic insights and design strategies toward the development of efficient and stable PSCs.