To achieve high efficiency, the blocking layer is of vital importance to perovskite solar cells. To investigate the influence of the morphology, conductivity, and photoluminescence quenching ability of the TiO2 blocking layers on device performance, three deposition methods (magnetron sputtering, spray pyrolysis, and spin coating) were adopted. High-quality TiO2 blocking layers should be homogeneous, highly compact, highly conductive, and efficient on photoluminescence quenching and electron extraction.