A unique sandwich-structured C/Ge/graphene composite with germanium nanoparticles trapped between graphene sheets is prepared by a microwave-assisted solvothermal reaction followed by carbon coating and thermal reduction. The graphene sheets are found to be effective in hindering the growth and aggregation of GeO2 nanoparticles. More importantly, the graphene sheets, coupled with the carbon coating, can buffer the volume changes of germanium in electrochemical lithium reactions. The unique sandwich structure features a highly conductive network of carbon, which can improve both the conductivity and the structural stability of the electrode material, and exemplifies a promising strategy for the development of new high performance electrode materials for lithium ion batteries. © 2013 The Royal Society of Chemistry.