Methylammonium lead iodide (MAPbI₃) perovskite solar cells using metal phthalocyanines (MPc) and naphthalocyanines (MNc) as hole transport materials for improving photovoltaic performance with long-term stability have been characterized. The purpose of this study was to fabricate and characterize MAPbI₃ perovskite solar cells using MPc and MNc as hole-transporting layers for improved photovoltaic and optical properties with stability. We characterized the photovoltaic characteristics, morphology, crystallinity and electronic structures of the MAPbI₃ perovskite solar cells using nickel phthalocyanine (NiPc). The photovoltaic performance reached the maximum values of conversion efficiency (η) at 13.4 %. The behavior was based on the surface morphology, crystal orientation and near-defect passivation of the perovskite crystal. The surface passivation of NiPc supported crystal growth, improving carrier diffusion with the suppression of near-defect carrier recombination. The photovoltaic mechanism was discussed using the energy diagram of the perovskite solar cell. The insertion of NiPc optimized the energy levels near the highest occupied molecular orbital while adjusting the valence band levels and supporting the charge transfer from the perovskite layer to the hole-transporting layer. Simulation using SCAPS-1D programs predicted the photovoltaic characteristics of the perovskite layer in terms of the hole-transporting thickness and trap density. The photovoltaic performance was optimized based on the results of the simulation and experiments.