Regulating Molecular Adsorption Configuration via Spatially Balanced Polarity for High‐Performance Inverted Perovskite Solar Cells

ABSTRACT Interfacial molecular adsorption configurations of the defect passivator are critical to the passivation efficiency and the performance of inverted perovskite solar cells (PSCs). However, the fundamental role of a molecule's internal polarity landscape remains poorly understood. By investigating para‐substituted benzenesulfonamides, we reveal that the electron‐withdrawing ‐Cl group in 4‐CBSA effectively offsets the internal dipole of the sulfonamide group, yielding a spatially balanced molecular dipole. This symmetric landscape promotes a stable parallel adsorption configuration and synergistic multi‐site coordination. In contrast, the electron‐donating ethyl group in 4‐EBSA induces an asymmetric polarity distribution, leading to disordered adsorption and limited passivation despite its higher absolute dipole magnitude. This optimized 4‐CBSA anchoring mitigates lattice distortion and residual tensile strain, while significantly suppressing nonradiative recombination. Consequently, 4‐CBSA‐modified inverted PSC, fabricated without a pre‐deposited hole transport layer by directly co‐depositing the self‐assembled molecule and perovskite onto the ITO substrate, achieves a champion efficiency of 26.14% (certified 25.23%) and excellent operational stability, retaining 97.23% of its initial performance after 1000 h of continuous maximum power point tracking. This work highlights the critical role of adsorption configuration in the rational design of molecular passivators for high‐performance and stable perovskite photovoltaics.