The graphene-coated carbon fiber cloth (CC@Gr) anchored with nanosized Co3O4 particles was successfully fabricated. According to the results of structural characterization, it was observed that the graphene-coated carbon fibers are able to anchor much higher amount of Co3O4 nanoparticles than graphene-free carbon fibers. The composite was applied as free-standing anode for lithium ion batteries, and it exhibits enhanced energy storage capability. A high reversible specific capacity of nearly 400mAhg−1 at a current density of 100mAg−1 can be achieved based on the total mass of Co3O4 and CC@Gr fibers (mass ratio=16:84). In addition, the composite demonstrates excellent rate performance and superior cycling stability.