V3O7·H2O@C core-shell materials have been synthesized using V3O7·H2O nanobelts as the cores and glucose as the source of carbon via an environmental hydrothermal method. The as-obtained V3O7·H2O@C core-shell materials were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR) and Raman spectrum. The influences of the reaction temperature, concentration of glucose and reaction time on the morphologies of the samples were respectively discussed in detail. The possible formation mechanism of V3O7·H2O@C was proposed according to our experimental results. Furthermore, the effect of V3O7·H2O and V3O7·H2O@C on the thermal decomposition of ammonium perchlorate (AP) were investigated by thermal gravimetric analyzer (TG) and differential thermal analysis (DTA). The thermal decomposition temperatures of AP in the presence of V3O7·H2O and V3O7·H2O@C were reduced by 70 and 89 °C, respectively, which indicates that V3O7·H2O@C core-shell composites have higher activity than V3O7·H2O.