This study demonstrates the formation and nanostructural behavior of self-assembled lipid/polymer materials in bulk and as thin films on silicon wafer surfaces. It investigates the freeradical polymerization of HEA within the nanoconfinement of GMO-based self-assembled structures. It further pioneers using in situ GISAXS, coupled with a liquid cell and UV-light reactor, to examine the structural response during photo-triggered HEA polymerization within confined nanostructures.