CH3NH3PbI3 perovskite solar cells using metal phthalocyanines (MPcs) with decaphenylcyclopentasilane (DPPS) are fabricated and characterized. The effect of addition of MPcs on the photovoltaic properties is investigated by changing the central element of the MPc and depositing MPc and DPPS successively on the perovskite layer. When silicon phthalocyanine is used to the cell, the microstructure of the perovskite film improves, which results in improvement of the open‐circuit voltage, fill factor, and photoconversion efficiency. For cells with only MPcs as the hole‐transport layer, the conversion efficiency increases by passivation with the phthalocyanine and crystal growth at room temperature.