Adsorbed surfactant bilayers on silica are proposed as the reaction site for the formation of ultrathin polystyrene films. Results from the polymerization of styrene in cetyl trimethyl ammonium bromide bilayers show effective conversion of adsolubilized monomer to polymer. The process has been demonstrated for a variety of precipitated silica substrates and for two types of initiation schemes. The polymer formed has been extracted and characterized using PA-FTIR, NMR, UV, and GPC. The molecular weight of polymer formed has also been investigated with respect to polymerization time.