In this paper, the effects of position of substrates in flames, preparation time, stability of flames and catalyst precursors on the synthesis of carbon nanofibers (CNFs) by ethanol catalytic combustion (ECC) were investigated. For investigating the effects of these influence factors on the synthesis of CNFs, several sets of controlled experiments were performed, such as preparation experiments with different position of substrates in flames, different preparation time, stable and unstable flames, and different catalyst precursors. In our experiments, the catalyst precursors were iron nitrate, cobalt nitrate, nickel nitrate, and iron chloride, cobalt chloride, nickel chloride. The as-synthesized products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. Our results indicate that the optimal position of substrates in flames is more than 1cm and less than 2.5cm, the optimal preparation time is more than 5min and less than 30min for massive yield, stable flames would be tent to synthesize CNFs with mainly single-type morphology and could improve the graphitization of CNFs, and the catalyst precursors obviously have effects on the synthesis of CNFs.