Lithium secondary batteries using carbon as negative electrode with intercalated Li have been developed. Various kinds of carbon fibers with different crystallographic and macroscopic structure are applied as a negative electrode for the lithium secondary batteries with 1 mol LiClO4/propylene carbonate electrolyte. The battery performances of the fibrous electrode are evaluated as a function of the structure of the carbon fibers. Not only the crystallographic structures but also the morphology of the fibers affect the battery performances. It was shown that Li is stored to form electrochemically the Ist stage compounds in well-ordered and even in disordered carbon fiber electrodes.