Recently, much attention has been attached to the material of cuprous iodide (CuI) single crystals. In this paper, a detailed study of the variation in the nucleation density and the growth of CuI crystals in silica gel as a function of the concentration of feed solution, pH of gel, gel aging time, growth temperature and volume of the feed solution is presented. The optimum conditions for growth of large size CuI single crystals in gel are: pH 5, concentration of complex 0.244M, gel aging 72h, temperature 45°C. A simple procedure for increasing the size of the crystals is adopted and the CuI single crystal with the size of 4mm3 is obtained. Also, the photoluminescence (PL) spectrum of as-grown CuI crystals in silica gel is evaluated by comparing its PL spectra with that of CuI crystals grown by solvent evaporation method. The results could provide a useful clue to further improve the properties of CuI single crystals.