Fabrication and characterization of CH₃NH₃PbI₃ (MAPbI₃) perovskite solar cells using copper phthalocyanine complex (CuPc) and tetracyanoquinodimethane (TCNQ) with decaphenylpentacyclosilane were performed. Effects of chemical group such as carboxyl or amino group in CuPc on the photovoltaic properties were investigated by changing the concentration. Incorporation of carboxyl-CuPc and TCNQ on the perovskite layer improved the short circuit current density related to conversion efficiency. The photovoltaic performance depended on the (100) crystal orientation and the surface coverage. The stability of the conversion efficiency was maintained for 30 days by suppression of decomposition of the perovskite layer using carboxyl-CuPc and TCNQ. The molecular interaction between CuPc and TCNQ was discussed by the molecular orbital and density of states near highest occupied molecular orbital and lowest unoccupied molecular orbital.