In this work, CO2 gas was used as a source of carbon to produce carbon nanofibers (CNFs). Sodium was used as a promoter to induce the formation of CNFs on a Ni/Al2O3 catalyst during a CO2 hydrogenation reaction. The,novel Ni-Na/Al2O3 catalyst not only effectively produced solid carbon from CO2 but also led to high reaction rates for the formation of CO. It was found that the added Na+ ions strongly covered the Ni surface. Calcination and reduction pretreatments led to new Na-related species that participated in the synthesis of CNFs. The structure of CNF materials obtained from CO2 varied with the reaction time and high-temperature thermal treatment. Initially, oxygen-rich functional groups, such as carboxylic acids, anhydrides, and phenols favored the formation of carbon. However, with increasing reaction times, the carbon growth became more graphite-like and oxygen-containing functional groups disappeared. The process of removal of oxygen-rich functional groups through a high-temperature treatment can lead to reduce the numbers of disorder sp(2) carbon materials and enhance the greater graphitic character for CNFs.