ABSTRACT It is promising to fabricate perovskite solar cells (PSCs) without antisolvent, but its intrinsic slow nucleation and unhomogenized growth are often accompanied by enormous solvated intermediates, which divert the α ‐FAPbI 3 crystallization and potentially restrict the acquisition of high‐performance PSCs. Herein, we present a balanced molecular interaction strategy using additives with mild dipole moments of around 1.9 Debye to suppress solvated intermediates. By systematically scrutinizing symmetric dimethyl isophthalate (DMIP) derivatives with varied groups (5‐H, ─F, ─Cl, ─Br, ─NH 2 , ─OCH 3 , and ─OH), the optimum phase‐evolution process is obtained with fluorine substituents. The balanced molecular interactions with Pb 2+ coordination, FA + hydrogen bonding, and I − between solvents and additives, significantly shorten t d‐α (the time for α ‐phase start to dominate) from > 150 to 23 s, enabling the faster and complete phase transformation to high‐quality α ‐FAPbI 3 . Consequently, we obtained a high‐power conversion efficiency up to 26.28%, representing the highest reported efficiency for antisolvent‐free regular PSCs based on pure FAPbI 3 absorbers. Moreover, the device maintains 93.7% of its initial efficiency after 1500 h aging at 85°C and retains 90% after 1000 h maximum power point tracking, demonstrating proper stability through this strategy.