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VO2(M) nanobelts were successfully synthesized using commercial V2O5, ethanol and water as the starting materials by a template-free hydrothermal method and subsequent calcination. The as-obtained products were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). Furthermore, the study on the influence of the as-prepared VO2(M) nanobelts on the thermal decomposition of ammonium perchlorate (AP) were evaluated by Thermo-Gravimetric Analysis and Differential Thermal Analysis (TGA/DTA), which showed the thermal decomposition temperatures of AP in the presence of the as-prepared VO2(M) nanobelts were reduced to 421 °C (decreased by 35 °C). The results indicated that VO2(M) nanobelts had great influence on the thermal decomposition temperature of AP.