Silica aerogels possess low thermal conductivity but have a brittle nature, while their polymers tend to exhibit enhanced mechanical properties. In this study, we introduce a new approach to overcoming this brittle property of silica aerogels. Polypropylene/silica aerogel composites were prepared by thermally induced phase separation followed by a supercritical CO₂ drying method. Silica aerogel was formed onto a polypropylene scaffold using a two-step sol-gel process with methyltrimethoxysilane as the silica precursor. Enhancement of the mechanical properties of the polypropylene/silica aerogel composite compared with a pristine methyltrimethoxysilane-based silica aerogel was observed. The effects of the latter on the microstructure and physical properties of the polypropylene/silica aerogel (hereafter referred to as the polymer matrix aerogel) composite were investigated. Compared with the polypropylene monolith, the polymer matrix aerogel composite demonstrated enhanced surface-chemical and microporous-structural properties such as higher hydrophobicity (135°), pore volume (0.18 cm³/g), average pore diameter (12.55 nm), and specific surface area (57.2 m²/g). This novel approach of incorporating methyltrimethoxysilane-based silica aerogel onto polypropylene when synthesizing the polymer matrix aerogel composite shows great potential as a durable superhydrophobic and corrosion resistant thermal insulating material.