Germanium-based materials has been considered as a promising anode material for Li-ion batteries due to their high theoretical capacity. Herein, we reported a novel Ge/GeO2-Reduced graphene oxide (GG-RGO) microcubes via one-step recombination using sodium borohydride as reductant, followed by a calcination process in reducing atmosphere. During the recombination, the reduced graphene oxide coated GeO2 nanoparticles self-assemble to form three-dimensional Ge shell/GeO2 core cubic structure. RGO coated construction can relieve volume expansion, provide a large reactive area and reduce distance for lithium diffusion. Meanwhile, two-phase Ge/GeO2 composite nanostructure can effectively increase specific capacity. Benefited from its unique three-dimensional structure, the Ge/GeO2-RGO composites exhibit high reversible capacity (1005 mAh g−1 at 100 mA g−1), good cycling stability (a high reversible capacity of 933 mAh g−1 after 50 cycles) and rate performance (740 mAh g−1 at 2000 mAh g−1).