A surfactant featuring a polymerizable pyrrole head group (dodecyl-dimethyl-(2-pyrrol-1-yl-ethyl)-ammonium bromide, DDPABr) was synthesized. The thermotropic behavior of the surfactant was investigated by differential scanning calorimetry (DSC) and X-ray scattering techniques, with small-angle X-ray scattering (SAXS) analysis revealing a highly ordered lamellar bilayer structure. After full characterization, DDPABr was used in the preparation of mesostructured SiO2 nanocomposite thin films via evaporation-induced self-assembly (EISA). Resulting thin SiO2- DDPABr films were studied by 1D and 2D small-angle X-ray scattering (SAXS) techniques, indicating a lamellar nanocomposite structure. Suitable theoretical SAXS models were applied to fit the experimental 1D SAXS data. The surfactant could be chemically polymerized within the lamellar domains.