Reducing organic groups on hydrophobic silica aerogels (SA) is worth exploring for lowering their thermal hazard risk. In this work, we used dimethyldichlorosilane (DMDCS) to modify silica alcogels, investigated the effects of DMDCS concentration and focused on the thermal hazard assessment of the DMDCS modified SA (DSA). It was turned out that the DSA had less -CH₃ content in spite of the thermal stability close to the trimethylchlorosilane modified SA (TSA), about 240 °C. The kinetics study suggested the apparent activation energy (E_a) could be divided into two segments, corresponding to the two processes in the pyrolysis. The positive enthalpy and entropy changes indicated that the thermal oxidation of the DSA was an exothermic reaction, which could not occur without external energy supply. The average E_a of the DSA was far larger than that of the TSA and the gross calorific value of the DSA decreased by about 12% compared with that of the TSA. All these results drew a conclusion that the DMDCS modified SA reduced the thermal hazard to some degree, which provided one possible solution to further lower the thermal hazard of hydrophobic SA.