The cyclic performance of a composite SiO and carbon nanofiber (CNF) anode was examined for lithium-ion batteries. SiO powder of several micrometers was pulverized using high energy mechanical milling. The SiO was ball-milled for 12h with CNF to produce a composite electrode material that exhibited excellent cycling performance. A reversible capacity of approximately 700mAhg−1 was observed after 200 cycles. The excellent cyclic performance was discussed with respect to the change of the valence state of Si by ball-milling. A large irreversible capacity at the first cycle for the SiO/CNF composite electrode was reduced to 2% by chemically pre-charging with a lithium film attached to the rim of the electrode.