The capacity of glycerol monooleate (GMO) to form a range of inverse-type liquid crystalline phases in excess water has been previously reported. They offer a unique platform for polymerization studies in nanoconfined water and lipid/water interfaces that have not yet been fully explored. Depending on the composition and temperature, the GMO self-assembles into a lamellar phase, inverse microemulsions, inverse hexagonal phase, and inverse bicontinuous cubic phases upon changing water content and temperature. The latter contains the gyroid-type (Ia3d) cubic and the diamond-type (Pn3m) cubic structure. They are complex three-dimensional structures with water nanochannels embedded in a lipid matrix. The Ia3d structure is observed at lower water content than the Pn3m structure, which can co-exist with excess water. A third primitive-type (Im3m) reverse bicontinuous cubic structure was also reported in the GMO/water system in the presence of the triblock copolymer F127. The three types of cubic structures are shown in Figure . More recently, the formation of thin films of lyotropic liquid crystalline structures was achieved through the physical adsorption of GMO on silicon wafer surfaces, followed by the evaporation of the solvent (ethanol) and hydration. The lamellar phase and the Ia3d-and Pn3m-type cubic structures were observed to form and transform inside the thin film upon increasing the relative humidity, leading to the hydration of the structures. The humidity threshold at which the cubic phase forms in the coating could be significantly lowered by adding additives, such as glycerol, that could interact with the water molecules in the channels and stabilize the cubic phase. A step forward was made by loading the nanostructured lipid coating with an antimicrobial peptide LL-37, creating bacteria-killing thin films on material surfaces. This study applies these films as a unique environment for polymerization studies directly at the water-film interface. In these films, the initiator, monomer, water, and light for polymerization only need to diffuse across sub-micrometers into the film, allowing for fast equilibration. Grazing incidence small angle X-ray scattering (GISAXS) can be used to study the film's structure. This offers a significant advantage over bulk SAXS studies, where the compounds and light must propagate several millimeters into the liquid crystalline phase. However, the substrate surface may influence the self-assembly and polymerization process. Hence, we combine bulk and film studies using transmission-, scanning-, and GI-SAXS to investigate the integration of the hydrophilic monomer hydroxyethyl acrylate (HEA) and its photopolymerization within the bicontinuous cubic phases. Poly-HEA is used, for instance, to make contact lenses and hydrophilic sponges. The hydrophilic initiator, lithium phenyl-2,4,6trimethylbenzoylphosphinate (LAP), was selected for its water solubility, initiation at 365 nm, and relatively low cytotoxicity. The integration of HEA in the aqueous channel of the cubic phase and HEA's conversion after polymerization were further evaluated with nuclear magnetic resonance spectroscopy (1H NMR).