The fundamental role of solubility and supersaturation of solute for crystal growth from solution has been widely realized. In order to optimize the process of CuI crystal growth by CuI·HI decomplexation in HI acid, the solubility and supersaturation curves of CuI in HI-H 2 O mixed solvent were measured, and then a modified concentration programming scheme was designed, which could grow high quality CuI single crystals of 2.5 mm on edge successfully. In this scheme, the concentration distribution of CuI·HI complex and HI acid in silica gel along their diffused direction were measured with spectrophotometer, and the evolution of CuI·HI complex supersaturation ratio was analysed. It was found that the excess CuI·HI complex concentration would lead to the high supersaturation ratio and the formation CuI dendrites. The condition for regular CuI single crystal growth in silica gel was measured as follow: when the crystal nuclei appears, the CuI·HI complex concentration in HI-H 2 O solvent should be kept in the range of 0.033-0.050 mol/L and its corresponding supersaturation ratio is 1.24-1.45, and then they should be respectively declined to a range of 0.025-0.033 mol/L and 1.14-1.26 at the stage of crystal growth. The results may provide a useful clue for further improvement of the experimental scheme.