Carbonyl-containing materials employed in state-of-the-art hybrid lead halide perovskite solar cells (PSCs) exhibit a strong structure-dependent electron donor effect that predominates in defect passivation. However, the impact of the molecular spatial conformation on the efficacy of carbonyl-containing passivators remains ambiguous, hindering the advancement of molecular design for passivating materials. Herein, we show that altering the spatial torsion angle of aromatic ketones from twisted to planar configurations, as seen in benzophenone (BP, 27.2 degrees), anthrone (AR, 15.3 degrees), and 9-fluorenone (FO, 0 degrees), leads to a notable increment of the electron cloud density around the carbonyl group, thus improving the passivation ability for lead-based defects. Consequently, the PSC performance also relies on the torsion angle of the aromatic ketones, with the coplanar FO-based PSC achieving a highest power conversion efficiency (PCE) of 25.13% and retaining 92% of its initial efficiency after 1000 h of operation at the maximum power point under continuous 1-sun illumination (ISOS-L-1I). Moreover, a perovskite mini-module (14.0 cm2) containing FO exhibits a PCE of 20.19%. Our findings highlight the influence of molecular conformation on the passivation effect of the carbonyl group, offering deeper insight into the design and development of aromatic ketones as passivators for highly efficient and stable PSCs.