In recent years, industrial explosion accidents are frequent, causing serious negative influences on society. Mechanical shock waves, as a typical destructive factor in explosion accidents, can cause serious personal injury and building damage. In addition, actual explosion accidents usually involve heat sources, harming protective materials and personnel. In this study, we designed SiO2-aerogel-modified polyurea and studied the effects of manufacturing pressure process and the concentration of SiO2 aerogel on the mechanical shock wave mitigation and thermodynamic properties of the modified polyurea. The results show that the addition of SiO2 aerogel can improve the mechanical shock wave mitigation performance of polyurea. The maximum peak overpressure and acceleration mitigation rate of the material has reached 17.84% and 62.21%, respectively. The addition of SiO2 aerogel helps to reduce the thermal conductivity of materials and improve the thermal insulation performance, and the atmospheric pressure process is more conducive to improving the thermal insulation performance of materials. The minimum thermal conductivity of the material has reached 0.14174 W/m·K, which is 45.65% lower than that of pure polyurea. The addition of SiO2 aerogel has different effects on the limiting oxygen index (LOI) of polyurea. Using a vacuum process, the LOI value increased with the increase in the SiO2 aerogel concentration, while using atmospheric pressure, the LOI value increased but is always lower than 21% and lower than pure polyurea. Thermogravimetric analysis showed that the addition of SiO2 aerogel under the vacuum process was helpful to improve the thermal stability of materials. However, atmospheric pressure would disrupt the thermal stability, manifested in a decrease in peak degradation temperature, an increase in peak degradation rate, and a decrease in residual mass.