Carbon nanofiber (CNF) supported cobalt oxide composites as high-capacity anode materials were prepared through a facile, effective method for potential use in rechargeable lithium-ion batteries. The effects of the calcining temperature on the crystallinity, grain size, specific surface area of Co 3O 4 and phase transformation from Co 3O 4 to CoO were studied in detail. Both the specific surface area and CNF content in CNF–cobalt oxide composites strongly affect the electrochemical performance of these series composites. The CNF–Co 3O 4 composite with 24.3% CNF pyrolyzed at 500 °C in Ar shows an excellent cycling performance, retaining a specific capacity of 881 mAh g −1 beyond 100 cycles. Homogeneous deposition and distribution of nanosized Co 3O 4 particles on the surface of CNF can stabilize the electronic and ionic conductivity as well as the morphology of Co 3O 4 phase, which may be the main reason for the markedly improved electrochemical performance.