Carbon/vanadium dioxide (C/VO2(B)) core–shell microspheres were prepared by a one-step hydrothermal process and characterized by X-ray diffraction and scanning electron microscopy. The electric cycling performance of C/VO2(B) in organic and LiCl aqueous electrolytes was evaluated by the galvanostatic method and by cyclic voltammetry, respectively. The results showed that the product had very stable cycling performance in both types of electrolytes compared to pure VO2(B).