Platelet graphite nanofibers (PGNFs) and turbostratic carbon nanofibers (TSCNFs) were synthesized by the pyrolysis of 3 and 10 vol% chloroform in ethanol, respectively, in the presence of Ni catalyst at 700 °C. Auger electron spectrometry analysis reveals that the participation of chloroform in the synthesis led to Ni–Cl bonding on the surface of the catalysts, resulting in a relatively poor crystalline layer and a coarse surface. Furthermore, the Ni–Cl compound affected the melting point and mobility of Ni, changing the morphology and geometrical shape of Ni particles. A low amount of chlorine in the catalyst led to the formation of smaller catalyst particles with a flat surface, resulting in graphene nanosheets stacked perpendicular to the fiber axis, which became PGNFs. In contrast, a high amount of chlorine in the catalyst led to the aggregation of the catalyst and thus the formation of large catalyst particles with a rough surface, resulting in the random stacking of graphene nanosheets, which became TSCNFs. The participation of chlorine was found to be important in the synthesis of the PGNFs and TSCNFs.