The dissipation of energy in the form of heat causes a huge energy loss across the globe. Thermal insulation materials which reduce heat loss can alleviate the energy crisis. Among many thermal insulation materials, silica aerogels (SAs) have attracted extensive attention due to their high surface area, low density and low thermal conductivity. However, the applications of SAs are restricted by their mechanical fragility. In this paper, a series of different ratios of silica–chitosan composite aerogels (SCAs) were prepared by mixing sodium silicate aqueous solution and chitosan solution followed by freeze drying. The surface morphology of SAs, CAs and SCAs was studied by scanning electron microscopy (SEM). The specific surface area, pore volume and pore size of the composite aerogels were studied by N2 adsorption–desorption isotherms. The thermal conductivities, chemical structures, thermal stabilities and hydrophobicities of SAs, CAs and SCAs were tested and analyzed. In addition, the adsorption properties of SCAs were measured using different organic solvents. The results reveal that when the proportion of sodium silicate aqueous solution and chitosan solution is 1:1, the obtained SCA−1/1 has the best performance, with a low thermal conductivity of 0.0369 W/m·K, a large specific surface area of 374.7 m2/g, and good thermal stability. In addition, the prepared SCAs also have good hydrophobicity and absorption properties, with adsorption capacities of 6.7–9.4 g/g, which show great application potential in the fields of insulation and adsorption.