The sorbitol improved mechanical properties while maintaining the textural structure of the silica aerogels. Herein, we report the silica aerogels reinforced with sorbitol via facile sol-gel polymerization. However, cross-linking with sorbitol enhances the mechanical properties while maintaining the highly textural structure, low density, and the thermal conductivity of silica aerogel. It is well known that although organically modified silica aerogels have enhanced mechanical properties, the specific surface area decreases due to the larger pore size. Our findings may contribute to tailor aerogels with specific functionality, as the springback effect has a direct influence on properties (e.g., porosity, pore size distribution), which is directly affected by the degree of re-expansion. Distinct changes of the X-ray scattering data were reproducibly associated with the shrinkage, re-expansion and drying of the gel network. Both show a porous fractal nanostructure, which partially collapses during drying and only recovers in surface-modified samples during the springback effect. Here, we report a multi-method approach focusing on in-situ X-ray scattering to observe alterations of the nanostructured material during the drying of surface-modified and unmodified silica gels. In this work, hydrophobic, monolithic silica aerogels with high specific surface areas were synthesized by modification with trimethylchlorosilane and ambient pressure drying. A multi-scale structural characterization of this significant volume change is key in controlling aerogel processing and properties. The drying of gels causes shrinkage, whereas re-expansion is believed to be linked to repelling forces on the nanoscale. The springback effect during ambient pressure drying of aerogels is an interesting structural phenomenon, consisting of a severe shrinkage followed by almost complete re-expansion.