To achieve tunable controls on the interactions of siliceous materials in subsurface environments bearing water and hydrocarbons, it is essential to determine the influence of hydrocarbon-water interfaces on the self-assembly of the silica particles. The hydrophilic silica particle have a tendency to aggregate on the water front of the interface. Self-assembly of silica nanoparticles proceeds via the migration of these nanoparticles to the water-hydrocarbon interface followed by aggregation at the interface. Fractal-like morphologies of assembled silica nanoparticles at water-hydrocarbon interfaces are observed. Rapid assembly of the hydrophilic silica nanoparticles at water-hydrocarbon interfaces corresponds to an overall reduction in the surface tension of water-toluene and water-heptane systems. These studies demonstrate the silica aggregation that is the precursor of silica polymerization, or nucleation and growth is influenced by the presence of hydrocarbons in subsurface geologic environments. These insights were derived from in operando ultrasmall and small-angle X-ray scattering (USAXS/SAXS) measurements, cryo-scanning electron microscopy (Cryo-SEM) imaging, and classical molecular dynamics simulations. These studies are intended to inform current and future efforts aimed at tuning silica reactivity in subsurface geologic environments to enhance permeability, the design and use of silica-based proppants to enhance fractures, and the development of effective strategies to control silica-based scaling behavior in subsurface reservoirs.