The influence of vanadium dioxide VO2(B) on thermal decomposition of ammonium perchlorate (AP) has not been reported before. In this contribution, the effect of VO2(B) nanobelts on the thermal decomposition of AP was investigated by the Thermo- Gravimetric Analysis and Differential Thermal Analysis (TG/DTA). VO2(B) nanobelts were hydrothermally prepared using peroxovanadium (V) complexes, ethanol and water as starting materials. The thermal decomposition temperatures of AP in the presence of I wt.%, 3 wt.% and 6 wt.% of as-obtained VO2<B) nanobelts were reduced by 39 °C. 62 °C and 74 °C, respectively. The results indicated that VO2(B) nanobelts had a great influence on the thermal decomposition temperature of AP Furthermore, the influence of the corresponding V2Os, which was obtained by thermal treatment of VO2(B) nanobelts, on the thermal decomposition of AP was also investigated. The resufs showed that VO2(B) nanobelts had a greater influence on the thermal decomposition temperature of AP than that of V2Os.