There are many candidate technologies that could be applied to the treatment of oil sands process-affected water (OSPW). Advanced oxidation processes (AOPs) are particularly useful for degrading biologically toxic or non-degradable materials such as aromatics, pesticides, petroleum constituents, and volatile organic compounds in wastewater. AOPs based on photocatalysis using nanomaterials are promising due to the high surface area, and exquisite tunability of surface chemistry afforded by the nanoparticles as well as the potential for harnessing sunlight as a passive, cost-effective energy source to initiate the reactions. However, application of these attractive materials in large-scale operations remains a challenge. To address these challenges, photocatalytic reactors have been proposed that utilize nanoparticle slurries or nanoparticles immobilized on various membrane supports. Ceramic membranes are often preferred because of their thermal and chemical stability. Recently, another class of support known as aerogels has attracted attention in absorption-based remediation. To date, there is a lack of reports in which these materials or nanomaterial hybrids have been applied as photocatalytic membranes. In this report, we present new hybrid silica aerogels that contain Si nanoparticles (SiNPs). The aerogels are produced using versatile and straightforward sol-gel reactions in the presence of SiNPs. Monoliths of the final SiNP-containing aerogel are obtained after drying in supercritical CO2 and have extremely high surface areas (>1,000 m2/g) as well as uniform and narrow pore structures. These hybrid aerogels offer distinct advantages of low density, high surface while maintaining the characteristics of immobilized SiNPs.