Abstract VO2(M) nanobelts encapsulated into carbon core–shell structured composite (VO2(M)@C) was successfully synthesized by the thermal treatment with the precursor V3O7·H2O@C composite under the inert atmosphere. The as-obtained sample was characterized by XRD, EDS, EA, FT-IR, Raman, SEM and TEM measurements. The core exhibited monoclinic phase VO2(M) and the carbon coated on the surface of VO2(M) was amorphous. The average thickness of carbon was about 18.5 nm. The possible formation mechanism of VO2(M)@C was proposed as that the reaction underwent the solid state reaction by the interface reaction between V3O7 core and carbon shell. Furthermore, VO2(M) and VO2(M)@C composite were explored as the cathode materials to apply in lithium-ion batteries, indicating that the VO2(M)@C composite electrode exhibited the better electrochemical properties than that of pure VO2(M), achieving the aim of improving the electrochemical properties of VO2(M).