Pb‐free halide perovskites have recently attracted immense attention due to the number of advantages in their optical and electronic properties. However, tuning the optical bandgap with minimized amounts of point defects is a particularly challenging task in photovoltaics. It is pivotal to clearly understand the detailed relationship between the bandgap change with defect generation and charge carrier lifetime. In this study, Cs ₃ Sb ₂ I ₉ crystals are synthesized by varied choice of solvents, namely, γ‐butyrolactone, a mixture of dimethylformamide and dimethyl sulfoxide, and hydroiodic acid. Although the same principles of decreasing solubility and crystallization are applied, Cs ₃ Sb ₂ I ₉ crystals with different size and shape in microscopic and macroscopic scale are obtained during heating and cooling of the solution. The synthesized crystals are investigated using a combination of different spectroscopies including Raman, UV–visible, and time‐resolved photoluminescence. In the results, it is suggested that there is a strong relationship between Urbach energy and the lifetime of charge carriers. In this research, readily applicable practical principles and examples of how to control the defects for the advancement in Pb‐free perovskite photovoltaics are provided.