The invention discloses a flexible graphene composite film and a preparation method thereof. The preparation method comprises the following steps of: based on oxidized or reduced graphene and organic polymer or micromolecule with a special functional group as raw materials, forming a uniform composite material by utilizing the interaction of a surface functional group of graphene and an organic molecule group, and preparing the graphene composite film on the surfaces of different substrates through methods of spin coating, spraying and the like. According to the preparation method disclosed by the invention, by utilizing an electron withdrawing group, an electron-donating group or a conjugate group in the organic polymer or micromolecule, the hole or electron concentration on the surface of a graphene electrode is increased, the work function of the electrode is controlled, the conductivity of the graphene electrode is improved, and the application range of a device is widened. According to the flexible graphene composite film disclosed by the invention, because the interaction among the groups is utilized, the compatibility of the prepared composite film is better, the structure is uniform, and the flexible graphene composite film is suitable for the photoelectric field of solar batteries, sensors, organic light-emitting diodes, touch screens and the like.