The electrochemical performance of a composite of nano-Si powder and a pyrolytic carbon of polyvinyl chloride (PVC) with carbon nanofiber (CNF) was examined as an anode for lithium-ion batteries. CNF was incorporated into the composite by two methods; direct mixing of CNF with the nano-Si powder coated with carbon produced by pyrolysis of PVC (referred to as Si/C/CNF-1) and mixing of CNF, nano-Si powder, and PVC with subsequent firing (referred to as Si/C/CNF-2). The external Brunauer–Emmett–Teller (BET) surface area of Si/C/CNF-1 was comparable to that of Si/C/CNF-2. The micropore BET surface area of Si/C/CNF-2 (73.86m2 g−1) was extremely higher than that of Si/C/CNF-1 (0.74m2 g−1). The composites prepared by both methods exhibited high capacity and excellent cycling stability for lithium insertion and extraction. A capacity of more than 900mAhg−1 was maintained after 30 cycles. The coulombic efficiency of the first cycle for Si/C/CNF-1 was as low as 53%, compared with 73% for Si/C/CNF-2. Impedance analysis of cells containing these anode materials suggested that the charge transfer resistance for Si/C/CNF-1 was not changed by cycling, but that Si/C/CNF-2 had high charge transfer resistance after cycling. A composite electrode prepared by mixing Si/C/CNF-2 and CNF exhibited a high reversible capacity at high rate, excellent cycling performance, and a high coulombic efficiency during the first lithium insertion and extraction cycles.