The effect of polymerization in the nanoconfinement versus in water was further analyzed based on the resulting polymer chain length and dispersity index using gel permeation chromatography (GPC). The results from this study contribute to the understanding of polymerization in lipid-based nanostructures, both in bulk structures and as thin films. They also clarify how confinement influences radical polymerization reactions, potentially guiding the development of advanced nanopatterned biomaterials.