A facile approach to the surface reduced graphene oxide (rGO) modification of micro-nano structured vanadium oxides composites are developed as cathode materials of lithium ions batteries (LIBs) and supercapacitors (SCPs) for the first time. The as-prepared V2O5–rGO and VO2–rGO composites exhibit remarkably enhanced cycling performance when being used as cathode materials in LIBs and SCPs, respectively. The uniform coating of graphene around the surface of vanadium oxides ensures good close electrical contact, therefore higher specific capacity and enhanced cycling performance than pure VO2 and V2O5 electrodes. Meanwhile, the cycling performance enhancement and capacity decay mechanism are presented, which is not only important to design electrode materials in LIBs and SCPs, but also extendable to the design and fabrication of other functional materials for energy storage and transfer systems.