Through the pyrolysis of acetylene at 250 °C, large quantities of carbon nanofiber bundles (CNFBs), curved carbon nanofibers (CCNFs) and helical carbon nanofibers (HCNFs) can be synthesized selectively by controlling the Fe:Cu molar ratio of Fe-Cu nanoparticles. In this study, the systematic experimental results indicated that the Cu content in the Fe-Cu nanoparticles and pyrolysis temperature had great impact on the yield and structure of the final samples. Moreover, the transmission electron microscopic observation indicated that the catalyst nanoparticles were enwrapped tightly by graphite layers, and the obtained HCNFs show good magnetic property. Compared to the methods reported in the literature, the approach described herein has the advantages of being simple, low-cost, and environment-friendly. It is suitable for the controllable and mass production of CNFBs, CCNFs and HCNFs.