Electrospinning is a fiber manufacturing process in which polymers are drawn and spun under the action of a high?voltage electrostatic field. This method has been widely used in material chemistry due to the simple preparation, low cost as well as easily available of micro?nano?scale fibers. In this paper, a polysulfur high?nucleus caged compound (Co48) constructed by thiacalixarene was used as the loading material, and polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) blend (PAN/PMMA) was used as the spinning support, Co9S8 nanoparticles loaded carbon nanofibers (Co9S8@CNFs) were prepared by electrospinning technique. Composite nanofibers were prepared by spinning carriers with PAN and PMMA mass ratios of 10∶0, 7∶3 and 5∶5, respectively, and the carbon nanofiber composites obtained after heat treatment were used as electrode materials for the study of lithium?ion battery materials. The addition of PAN and PMMA has a positive effect on the electrochemistry of the final product compared to the calcined product of Co48 crystals. The composites fabricated from PAN and PMMA presented high specific capacity,good cycling stability and rate capability.