Metastable vanadium dioxide/carbon (VO2(B)/C) nanobelts have been successfully synthesized via a facile surfactant-free hydrothermal method using V2O5 and sucrose as reactants. The VO2(B)/C with carbon content of 0.96wt.% shows well-distributed nanobelt morphology with an average width of 120–200nm, thickness of 40–60nm and length of 1–3μm. The nanobelts exhibit preferable electrochemical performances with high initial discharge capacity, good cycling stability and excellent high-rate performance. The initial discharge capacity can reach 218.6mAhg−1, and maintain 152.6mAhg−1 after 100 cycles at 50mAg−1. When the current density increases to 1000mAg−1, the discharge capacity is still as high as 138.2mAhg−1. VO2(B)/C nanobelts would be a promising cathode material for lithium ion batteries.