This study explores the influence of molar ratio of the synthetic solution of methylammonium iodide (MAI) and PbI2 on perovskite solar cells. The complete perovskite crystals must be produced in a low-humidity environment. The substrate is spin-coated in the adjusted MAPbI3 synthesis solution and annealed by using a nitrogen furnace tube to form perovskite crystals. During the crystallization of MAPbI3, some of the PbI2 remains, which improves the efficiency of the perovskite solar cell. Therefore, we adjust the molar concentration of MAI to find the appropriate amount of the PbI2 residual. We fix the MAI molar concentration at 1 M and adjust the PbI2 molar concentration from 0.8 M to 1.4 M. The molar ratios of MAI and PbI2 are, then, 1:0.8, 1:1, 1:1.2, and 1:1.4, respectively. Then, we use UV–vis, FE-SEM, and photoelectric conversion efficiency (PCE) measurements for comparing the growth of perovskite crystals and their photoelectric characteristics. The results show that 1.2 M of PbI2 is the most appropriate concentration for perovskite solar cells among the adjusted concentrations.