The utility of planar supported lipid bilayers (PSLBs) as protein-resistant coatings in molecular device technologies is hampered by the chemical and mechanical instability of these structures relative to (for example) alkylsiloxane self-assembled monolayers. We have been investigating cross-linking polymerization of diene-functionalized lipids as a strategy to enhance the inherent instability of PSLBs. The membranes are self-assembled by vesicle fusion, then polymerized in situ by a redox-initiated chemistry. In contrast to diacetylene-based materials, these new diene-based materials contain relatively few defects. They are stable to conditions that would destroy a fluid membrane (e.g. exposure to air, surfactants, solvents), yet retain the characteristic protein resistance of a fluid PSLB. Thus these structures appear to possess both the stability and inertness required for implementation of PSLBs in many technological applications. This talk will focus on preparation, characterization, and protein functionalization of diene-based PSLBs.