The invention discloses a preparation method of three-dimensional graphene or a composite system thereof. The preparation method comprises the steps of: by taking a transition metal elementary substance and/or a compound containing a transition metal element as raw materials, preparing a three-dimensional porous metal catalyst template through high-temperature reduction; growing the three-dimensional graphene by utilizing a chemical vapor phase deposition method to obtain the three-dimensional graphene with a catalyst framework; furthermore, etching the three-dimensional graphene with the catalyst framework to obtain three-dimensional graphene powder; and furthermore, compositing the three-dimensional graphene powder with metal, a macromolecular material, a biomolecular material and the like to form a composite material system. The preparation method is simple in technique, capable of fast and massively preparing high-quality and high-density three-dimensional graphene or composite material thereof, and has wide application prospects on the aspects of water treatment, biomedicines, energy generation and conversion and energy accumulation devices, static resistance, thermal management, heat conduction and dissipation, sensors, electromagnetic shielding, wave absorption, catalysis and the like.