We report the catalytic effect on the synthesis of multiwalled carbon nanotubes (CNTs). The CNTs were grown vertically aligned on the iron (Fe), cobalt (Co), and nickel (Ni) catalytic nanoparticles deposited on alumina substrates by thermal chemical vapor deposition (CVD) of acetylene in the temperature range 900–1000 °C. We also synthesized them on the silicon oxide substrates by pyrolyzing iron phthalocyanine (FePc), cobalt phthalocyanine (CoPc), and nickel phthalocyanine (NiPc) at 700–1000 °C. In both syntheses, the CNTs grown using Fe exhibit about 2 times higher growth rate than those using Co and Ni. As the temperature rises from 700 to 1000 °C, the growth rate of CNTs increases by a factor of 45. The Arrhenius plot of growth rates provides the activation energy 30 ± 3 kcal/mol for all three catalysts, which is similar with the diffusion energy of carbon in bulk metal. It suggests that the bulk diffusion of carbon would play a decisive role in the growth of CNTs. The diameter of CNTs is in the range of 20–100 nm, showing an increase with the temperature. As the diameter is below 30 nm, the CNTs usually exhibit a cylindrical structure. The CNTs were intrinsically doped with the nitrogen content 2–6 atomic%. The degree of crystalline perfection of the graphitic sheets increases with the temperature, but depends on the catalyst and the nitrogen content. The graphitic sheets of CNTs grown using Fe are better crystalline than those grown using Co and Ni. As the nitrogen content increases, the degree of crystalline perfection decreases and the structure becomes the bamboolike structure probably due to a release of strains.