This study deals with the possible applications of three-dimensional foam-like graphene structures. Starting from a Ni porous structure, the deposition of graphene is performed by Chemical Vapour Deposition (CVD) process on commercial Ni foam scaffolds. Then, in order to guarantee mechanical support for the successive steps, Poly-Methyl MethAcrylate (PMMA) is infiltrated and, successively, the Ni is etched. In this way, a hollow free-standing graphene foam with pores filled with PMMA is formed. Subsequently, by infiltrating a polymer into a hollow graphene structure, it is possible to obtain a three-dimensional (3D) graphene foam (GF)/polydimethylsiloxane (PDMS) composite. At the end of the process, PMMA is removed in an acetone solution.