AbstractFurther minimizing the defect state density in the semiconducting absorber is vital to boost the power conversion efficiency of solar cells approaching Shockley-Queisser limit. However, it lacks a general strategy to control the precursor chemistry for defects density reduction in the family of iodine based perovskite. Here the alkaline environment in precursor solution is carefully investigated as an effective parameter to suppress the incident iodine and affects the crystallization kinetics during film fabrication, via rationale adjustment of the alkalinity of additives. Especially, a ‘residual free’ weak alkaline is proposed not only to shrink the bandgap of the absorber by modulating the stoichiometry of organic cation, but also to improve the open circuit voltage in the resultant device. Consequently, the certified efficiency of 20.87% (Newport) is achieved with one of the smallest voltage deficits of 413 mV in the planar heterojunction perovskite solar cell.