Polystyrene (PSt) or poly(vinylbenzyl chloride) (PVBC) crosslinked with divinylbenzyl (DVB) materials were synthesized through free radical polymerization into templates formed by the surfactant polyoxyethylene (4) lauryl ether (Brij-30). The chemical composition of the final products was verified through attenuated total reflectance infrared spectroscopy (ATR-IR) and the thermal behavior was investigated through thermogravimetric analysis (TGA). Depending on the organization of Brij-30 in aqueous solution, three characteristic structures, namely spherical nanoparticles, platelet-like objects and three-dimensional networks, were identified through scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The spherical nanoparticles and the platelet-like objects form rather stable dispersions, especially in aqueous surfactant solutions, as exemplified by the evolution of the turbidity of the PSt-based materials, using sodium dodecyl sulfate as surfactant. All materials retain their integrity even after thermal treatment at high temperature (200-2508C). The benzyl chloride group of the PVBC-based materials offers a significant potential for further elaboration and practical applications, since they can be further functionalized while retaining their integrity. This potential is demonstrated here through hydrolysis to obtain hydroxyl-functionalized three-dimensional networks.