The practical application of silica aerogels is an enormous challenge due to the difficulties in improving both mechanical property and thermal insulation performance. In this work, silk fibroin was used as scaffold to improve the mechanical property and thermal insulation performance of silica aerogels. The ungelled SiO2 precursor solution was impregnated into silk fibroin to prepare silk fibroin–SiO2 composite aerogels via sol−gel method followed by freeze-drying. By virtue of the interfacial hydrogen-bonding interactions and chemical reactions between silk fibroin and silica nanoparticles, SiO2 was well-dispersed in the silk fibroin aerogel and composite aerogels exhibited enhanced mechanical property. By increasing the loading of silk fibroin from 15 wt % to 21 wt %, the maximum compressive stress was enhanced from 0.266 to 0.508 MPa when the strain reached 50%. The thermal insulation performance of the composite aerogels was improved compared with pure silica aerogel, as evidenced that the thermal conductivity was decreased from 0.0668 to 0.0341 W∙m‒1∙K‒1. Moreover, the composite aerogels exhibited better hydrophobicity and fire retardancy compared to pure silica aerogel. Our work provides a novel approach to preparing silk fibroin–SiO2 composite aerogels with enhanced mechanical property and thermal insulation performance, which has potential application as thermal insulation material.