Disastrous oil spills cause severe environmental issues. The shortcomings of current cleaning methods for remediating oil have prompted the latest research drive to create intelligent nanoparticles that absorb oil. We, therefore, synthesized 197 ± 50 nm floatable photoreactive hybrid nanoparticles with Ag–TiO2 plasmonic photocatalyst (Eg = 3.08 eV) content to eliminate interfacial water pollutants, especially toluene-based artificial oil spill. We found that the composite particles have non-wetting properties in the aqueous media and float easily on the surface of the water due to the moderate hydrophobic nature (Θ = 113°) of the matrix of polystyrene, and these properties lead to elevated absorption of the interfacial organic pollutants (e.g., mineral oil). We showed that (28.5 mol%) divinylbenzene cross-linker content was required for adequate swelling capacity (2.15 g/g), whereas incorporated 15.8% Ag–TiO2 content in the swollen particles was enough for efficient photodegradation of the artificial oil spill under 150 min LED light (λmax = 405 nm) irradiation. The swollen polymer particles with embedded 32 ± 7 nm Ag–TiO2 content increase the efficiency of photooxidation by increased the direct contact between both the photocatalysts and the artificial oil spill. Finally, it was also presented that the composite particles destroy themselves: after approximately one and a half months of continuous LED light irradiation, the organic polymer component of the composite was almost completely (88.5%) photodegraded by the incorporated inorganic photocatalyst particles.