Abstract: PAN@graphene core-shell nanofibers were synthesized by the chemical vapor deposition method with PAN-based carbon nanofibers as the raw material and Cu foils as the catalyst. The morphology, structure, and components of the as-prepared PAN@graphene nanofibers were characterized by scanning electron microscopy, transmission electron microscopy and Raman spectroscopy analysis. The results showed that the core-shell structure was constructed with graphene films coating the PAN-based carbon nanofibers, and the one-dimensional graphene fiber was synthesized by the film-scrolling technique. In addition, the electrochemical performance of the graphene fiber was tested. The calculated specific capacitance value of graphene fiber was 158 mF/cm³ at the scanning rate 10 mV/s, and the excellent flexibility after multiple bending in a gel electrolyte of PVA/H₃PO₄.