Fabrication and characterization of the photovoltaic and optical properties, and microstructure of perovskite-based solar cells with lead phthalocyanine (PbPc), zinc phthalocyanine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and copper(I) thiocyanate as hole-transporting layers were investigated. X-ray diffraction analysis and energy-dispersive X-ray spectroscopy were used to identify surface morphologies of the crystal structure and the elemental composition. Introducing PbPc into perovskite solar cells extended the retaining period of photovoltaic activity and performance. The effects of the hole-transporting layer on incident photon-to-current efficiency were investigated. The energy diagram and photovoltaic mechanism of the perovskite solar cells with the hole-transporting layer are discussed.