Abstract: Graphene has extremely high in-plane thermal conductivity. Adding graphene into polymer substrate can significantly improve the thermal conductivity of the polymer. By constructing a three-dimensional network of the graphene can form more thermal conductivity channels in the composite, and in further improve the material thermal conductivity. The three-dimensional network graphene thermal conductive composites have many kinds of preparation methods and simple process. The preparation methods of three-dimensional network graphene thermal conductive composites including 3D printing method, magnetic field orientation method, electric field orientation method, lyophilized orientation method and self-assembly method are reviewed. The principles of three-dimensional network construction, advantages and disadvantages of different preparation methods and their effects on the thermal conductivity of materials are described. The current shortcomings of such material preparation are summarized, and the future research direction is prospected.