Abstract Perovskite solar cells (PSCs) have attracted extensive attention in the photovoltaic field, with their highest power conversion efficiency (PCE) reaching 26%. However, the commercialization of PSCs is severely hindered by the instability of precursor solutions and the narrow annealing window for perovskite films. Here, 2,3,5‐trichlorobenzaldehyde (3Cl‐BZH) is introduced into the organic salt precursor solution to eliminate excess organic amines through Schiff‐base reactions, avoiding subsequent irreversible amine‐cation reaction of formamidine‐methylammonium (FA‐MA + ) and improve the stability of the precursor solution. Meanwhile, the chemical interaction between C═O group of 3Cl‐BZH and formamidinium (FA + ) in the perovskite precursor contributes to the slow release of organic ions, which reduces the reaction rate between organic salt and PbI 2 , retarding the crystallization of perovskite film. The PSCs with a conventional annealing process achieve a champion efficiency of 24.08%, which derives from the defect passivation effect of 3Cl‐BZH. The PSCs with an ultrawide annealing window of 240 h for wet perovskite film in the air still maintain an efficiency of 22.01%. The aging‐resistant precursor and ultrawide annealing window are beneficial for reproducible, efficient, and low‐cost PSCs, which brings great prospects for the commercialization of PSCs.