A novel VO2(B)-multiwall carbon nanotube (MWCNT) composite with a sheet-like morphology was synthesized by a simple in situ hydrothermal process. The morphology and structural properties of the samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). FE-SEM observations demonstrated that the nanosheets are frequently grown together in the form of bundles composed of numerous nanosheets, each with a smooth surface and a typical length of 300–500nm, width of 50–150nm, and thickness of 10–50nm. Electrochemical measurements were carried out using different discharge cut-off voltages. Electrochemical tests show that the VO2(B)–MWCNT composite cathode features long-term cycling stability and high discharge capacity (177mAhg−1) in the voltage range of 2.0–3.25V at 1C with a capacity retention of 92% after 100 cycles. The electrochemical impedance spectra (EIS) indicate that the VO2(B)–MWCNT composite electrode has very low charge-transfer resistance compared with pure VO2(B), indicating the enhanced ionic conductivity of the VO2(B)–MWCNT composite. The enhanced cycling stability is attributed to the fact that the VO2(B)–MWCNT composite can prevent the aggregation of active materials, accommodate the large volume variation, and maintain good electronic contact. We strongly believe that the VO2(B)–MWCNT composite can be considered as a potential cathode material for lithium-ion batteries.