It has been found that carbonaceous materials containing a transition metal coordinated by 4 nitrogens in the square-planar configuration (metal–N4 site) on the surface possessed a catalytic activity for various electrochemical reactions related to energy conversion and storage; i.e., oxygen reduction, hydrogen evolution, and quite recently, the electrode reactions in vanadium redox flow batteries (VRFB). The catalyst for the VRFB positive electrode discharge reaction, i.e., the dioxovanadium ion reduction, was formed by coating the surface of cup-stack carbon nanotubes with a carbonaceous thin film with the Fe–N4 site generated by the sublimation, deposition, and pyrolysis of iron phthalocyanine. In this study, the influence of the physical properties of the catalyst on the electrochemical reactions was investigated to optimize the coating. With an increase in the coating, the specific surface area increased, whereas the pore size decreased. The surface Fe concentration was increased in spite of the Fe aggregation inside the carbon matrix. The catalytic activity enhancement was achieved due to the increase in the specific surface area and the surface Fe concentration, but was lowered due to the decrease in the pore size, which was disadvantageous for the penetration of the electrolyte and the mass transfer.