A flexible carbon nanofiber film with high conductivity was prepared by electrospinning, and then Cu was uniformly deposited on the fiber film by pulse electrodeposition to prepare Cu nanocrystal/carbon nanofiber film. Cu@PtCu/carbon nanofiber (Cu@PtCu/CNF) catalytic films were synthesized by in-situ substitution reduction. The Cu@PtCu/CNF catalytic film solves the problem of uneven activity of the catalytic layer and can be directly used as the catalytic layer. The morphology and structure were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Electrochemical test results show that the Cu@PtCu/CNF catalytic films obtained at the chloroplatinic acid concentration of 0.5 mg·mL