A stable, substrate-supported phospholipid film was created by in-situ photopolymerization of an acrylate functionalized lipid assembly. The lipid film was generated on alkylated substrates by vesicle fusion and polymerized by irradiation with visible light, using eosin Y/triethanolamine as the photoinitiating species. Optimal experimental conditions were determined with respect to vesicle fusion time and duration of irradiation. The resulting polymeric lipid film was characterized by contact angle measurements, angle-resolved ESCA, and polarized external reflectance infrared spectroscopy. Static stability and desorption studies indicate enhanced stability of the photopolymerized system when compared with a heat-initiated analogue prepared by classical free-radical techniques.