The invention discloses a porous graphene/polymer composite structure, and a preparation method and application thereof. The composite structure mainly comprises a compound formed by porous graphene and more than one polymer and/or polymer monomer. The preparation method comprises the following steps of: compounding polymers and/or polymer monomers with porous graphene to form a target product, wherein the compounding manner comprises single-screw/double-screw fusing processing, injection molding, blow molding, melt spinning, solution spinning, electrostatic spinning, electrostatic spraying, powder metallurgy, liquid mixing or high speed mechanical stirring dispersion. The invention is simple in process, wide in source of raw materials, easy to implement in large scale, low in cost, safe, environment-friendly and free from toxic and harmful wastes, and the product obtained is excellent in thermal and electric properties, and has wide application prospect in the fields of heat conduction, radiation, electric conduction, anti-static electricity, electromagnetic shielding and the like.