The application of polymeric materials with uniformly controlled nanostructures templated with hexagonal lyotropic liquid crystals (LLCs) has potential applications in separation technology. The hexagonal LLCs with closely packed columnar structures which will in turn result in high pore density and narrow pore size distribution in polymeric materials are important for high permeability and selectivity. However, retaining hexagonal LLC structure in polymeric materials is entropically difficult and often the morphologies generated are not the same as the original LLC structure. In this study, structure retention in cross-linked poly(ethylene glycol) diacrylate (XPEGDA) templated with hexagonal LLCs formed from ionic or non-ionic surfactant has been achieved by controlling the surface tension, reinforcing the polymeric material by a silica network, or combining these two methods by using volatile solvent with low surface tension associated with silica network reinforcement. Polymer materials templated from hexagonal LLCs not only have potential applications as nanofiltration but also in many other fields like tissue engineering, catalysis and electrodes.