CNF5@Co-CoO (CNFs = carbon nano-fibers) composite showing "gypsophila"-like morphology was designed and prepared for the first time with in situ grown PAN@ZIF-67 (PAN = polyacrylonitrile) as the precursor. Benefiting from its unique morphology, hierarchically porous structure, and high-activity Co-CoO catalyst centers, the composite shows a better electrochemical performance than pure CNFs as a cathode for Li-O-2 batteries.