AuNP/PDMS nanocomposites have been synthesized in the form of gels, foams, and films with distinctive structure and morphology. A simple in situ process in aqueous medium for the formation of such composite materials is described. The nanoparticles are held firmly within the PDMS while still being chemically accessible to substances soluble in PDMS. We demonstrate the utility of this property for water purification applications such as removing aromatic solvents and sulfur‐containing contaminants from water. The contaminants can be freed from the composite with a simple thermal treatment, allowing the material to be reused. We also demonstrate chemically selective uptake and release of a fluorescent dye by the nanocomposite as a drug delivery model system.