Due to the high electrical conductivity and chemical inertness, graphene has been widely incorporated into the copper matrix to form the reinforced composites. However, graphene is prone to agglomerate. In addition, uniform dispersion between graphene and copper cannot be obtained due to the differences of density. In this study, in order to fabricate high electrical conductivity and superior anticorrosion performance Graphene/copper composites, the rational design of the microstructure of graphene within the matrix is investigated. First, high-quality graphene films were grown on the surface of copper powder by thermal CVD, followed by vacuum hot-pressing to fabricate graphene/copper composites. The composites were characterized by Raman and XRD spectra, and the electrical conductivity was determined by Eddy current tester. The comparison of anticorrosion performance was carried out by measuring the weight loss of the samples as the function of etching time by self designed device. Both Copper and Graphene/Copper samples exhibit typical crystal faces (111), (200), and (220) via XRD. A cellular graphene framework was created at the grain boundary in the composites. The composites exhibit high electrical conductivity of 96%IACS, which is higher than that of reported graphene/copper composites. In addition, our graphene/copper composites also have superior corrosion resistance property against wet corrosion in copper etchant, achieving 37.6% improvement compared to the bare copper. In conclusion, we developed a facile process for the synthesis of copper matrix composites embedded with cellular graphene framework. The obtained composites have a high electrical conductivity and superior anticorrosion performance.