A new design and fabrication of anode materials with perfect synthesized performance has been developed. The carbon fibers (CFs) are well suited for multifunctional lightweight design because of the high specific tensile stiffness, ultimate tensile strength (UTS), and high lithium (Li)-intercalation capability. Thus, the CFs can integrate the structural reinforcement part with the battery electrode to store the energy. However, the limitation of low theoretical capacity of commercial CFs for the structural lithium-ion battery (SLIB) is an urgent issue that should be settled. Therefore, this work compounds a novel CFs@Co3O4 composite, which has been successfully fabricated by thermal treatment of CFs@ZIF67 precursor. The performances of the as-prepared products have been enhanced by covering the cobaltic oxide polyhedra firmly on CFs to form a synergetic electrode. The as-obtained CFs@Co3O4 possess well-defined porous structure, which exhibits excellent Li storage properties including high reversible capacity of 420mAhg−1 at 100mAg−1 without obvious decay up to 150cycles (a huge increase as high as 282% than that of the CFs). Furthermore, this work demonstrates a facile and affordable preparation of other CFs@metal oxide composites that hold great promise in the field of energy storage and will become the promising candidate anode materials for SLIBs.