This study improved quality of CH3NH3PbI3 (MAPbI3) perovskite films by delaying thermal annealing in the spin coating process and introducing KI and I2 to prepare MAPbI3 films that were low in defects for high-efficiency perovskite solar cells. The influences of delayed thermal annealing time after coating the MAPbI3 perovskite layer on the crystallized perovskite, the morphology control of MAPbI3 films, and the photoelectric conversion efficiency of solar cells were investigated. The optimal delayed thermal annealing time was found to be 60 min at room temperature. The effect of KI/I2 additives on the growth of MAPbI3 films and the corresponding optimal delayed thermal annealing time were further investigated. The addition of KI/I2 can improve perovskite crystallinity, and the conductivity and carrier mobility of MAPbI3 films. Under optimized conditions, the photoelectric conversion efficiency of MAPbI3 perovskite solar cells can reach 19.36% under standard AM1.5G solar illumination of 100 mW/cm2.