<p>Perovskite solar cells were fabricated and characterized using phthalocyanine and naphthalocyanine. These materials offer great advantages for application in photovoltaic devices in light of their electronic and optical properties, and heat and chemical resistance. Performance enhancement and long-term stability are possible through control of the center atom and substituents in phthalocyanine and naphthalocyanine. This research is focused on characterization of a perovskite solar cell using naphthalocyanines with chemical substituents on the axial ligand. The photovoltaic characteristics, optical properties, morphologies, crystallinity, and trap density were measured. In the system utilizing lead naphthalocyanine with chlorine substituents on the axial ligand, the open-circuit voltage and conversion efficiency were improved. Introduction of germanium and silicon naphthalocyanines bearing hydroxyl groups passivated the perovskite layer, improving the charge transfer and carrier diffusion. The crystal grain growth and orientation in the perovskite layer were confirmed through morphological observation using optical microscopy, scanning electronic microscopy, and energy-dispersive x-ray spectroscopy, as well as structural analysis via x-ray diffraction. The naphthalocyanines exhibited absorption in the ultraviolet–visible–near-infrared region, and showed a bandgap in the range of 1.08&#xa0;eV to 1.45&#xa0;eV. The photovoltaic mechanisms were evaluated through experimental results and energy level diagrams of the perovskite solar cell. Optimization of the energy levels in the highest occupied molecular orbital and lowest unoccupied molecular orbital and the bandgap of the naphthalocyanines support charge transfer and carrier diffusion while suppressing recombination near the interface of the perovskite crystal and hole transport layer.</p> Graphical Abstract <p></p>