The invention belongs to the field of polymer composite materials, and in particular relates to a composite conductive film taking graphene as a conductive agent and a preparation method of the composite conductive film. The composite conductive film is prepared by premixing polyvinyl chloride and graphene and then performing mixing in a double-roll mixing mill. The preparation method comprises the steps of firstly, adding a stabilizing agent and a plasticizing agent into polyvinyl chloride resin, stirring uniformly, and then curing the mixture in a drying oven; then, adding graphene into the mixture, and stirring uniformly; finally, mixing in the double-roll mixing mill to obtain a graphene/polyvinyl chloride composite conductive film, wherein the content of two-dimensional graphene in the composite material is 0.5-4.5wt%. The polymer base conductive composite material taking graphene as the conductive agent, provided by the invention, has the characteristics of light weight, corrosion resistance and adjustability resistivity on a large scale and the like, and is easy to process, so that the composite material can be widely applied to the modern electronics industry, information industry and high-tech fields. The composite conductive film disclosed by the invention is simple in process, high in production efficiency and easy in implementation of industrial large-scale production.