A facile and green method is developed to fabricate Fe3O4–Fe nanowires with a large amount of nanoholes directly grown on highly conductive nanofiber arrays. By electrodeposition of Fe clusters on C/TiC nanofiber array, followed by in-situ chemical conversion of Fe to FeC2O4–Fe nanowires and the thermal decomposition of FeC2O4–Fe to Fe3O4–Fe, a Fe3O4–Fe nanocomposite electrode with unique architecture is successfully prepared. The electrode is characterized by means of X-ray diffractometer, scanning electron microscope and transmission electron microscope. Electrochemical properties of the nanowire arrays electrode as the anode of lithium-ion batteries are examined by cyclic voltammetry and galvanostatic charge/discharge test. The electrode displayed remarkably high capacity, excellent high rate performance and superior cycling stability. The reversible capacity of the electrode reached 1012 mAh g−1 at 1C and retained to be 500 and 255 mAh g−1 at 10 and 20C, respectively. It can still deliver a specific capacity of 100 mAh g−1 even at 50C (72 s charge–discharge). The electrode also has a satisfactory cycling performance with capacity retention of 93.9% after 100 cycles at 1C. The magnificent performance can be attributed to the distinct configuration resulting from the novel fabrication process.