Carbon nanofiber (CNF)/3D nanoporous (3DNP) Si hybrid materials were prepared by chemical etching of melt-spun Si/Al-Cu-Fe alloy nanocomposites, followed by carbonization using a pitch. CNFs were successfully grown on the surface of 3DNP Si particles using residual Fe impurities after acidic etching, which acted as a catalyst for the growth of CNFs. The resulting CNF/3DNP Si hybrid materials showed an enhanced cycle performance up to 100 cycles compared to that of the pristine Si/Al-Cu-Fe alloy nanocomposite as well as that of bare 3DNP Si particles. These results indicate that CNFs and the carbon coating layer have a beneficial effect on the capacity retention characteristics of 3DNP Si particles by providing continuous electron-conduction pathways in the electrode during cycling. The approach presented here provides another way to improve the electrochemical performances of porous Si-based high capacity anode materials for lithium-ion batteries.