Carbon nanotubes (CNTs) have been interested in various area such as electronics, photonics, energy devices, and other applications. However, it has been a long-standing challenge to establish a straightforward process for the production of uniform CNTs with desired structures and properties. Here, we have fabricated hybrid carbon films which are composed of carbon nanotube arrays grown on reduced graphene oxide films. The processes enabled the formation of diameter, wall-number, and atomic structure controlled carbon nanotube arrays. This method enabled to fabricate the Fe-porphyrinic CNTs, which are outstanding oxygen reduction catalysts via the efficient 4-electron oxygen reduction process. The cyclic and the rotating disk electrode (RDE) voltammograms confirmed the outstanding oxygen reduction reaction (ORR) properties of the Fe-porphyrinic CNT. The fabrication processes of the efficient, bio-mimetic, rigid, electron-conducting carbon nanotube catalysts can have a significant impact on the wide deployment of the current PEMFC technology.