The invention discloses a composite multilayer anti-corrosion film and application thereof. The composite multilayer anti-corrosion film comprises a metal adhesion layer, a metal anti-corrosion layer,a conductive ceramic amorphous layer, a conductive ceramic crystallizing layer and a carbon covering layer from bottom to top. The ingredients of the metal adhesion layer and the anti-corrosion layerare not completely identical. According to the composite multilayer anti-corrosion film and the application thereof, in order to effectively combining the advantage of good conductivity of metal andthe advantage of better durability of conductive ceramics, corrosion resistant metal and conductive ceramics are introduced. In order to achieve the composite effect, the metal adhesion layer is further introduced to achieve growth of a coating of the corrosion resistant metal, and the crystallinity of the conductive ceramic crystallizing layer above the metal adhesion layer is improved by introducing the conductive ceramic crystallizing layer; and the crystal boundary intervals of polycrystalline ceramics are covered with a carbon covering layer, good density is achieved, thus a multilayer film structure with conductivity and corrosion resisting performance is constructed, the application range is wide, and the composite multilayer anti-corrosion film has positive promotion significance on the research and development of proton exchange membrane fuel cells.