Mixed monolayer surfactant films of perfluorotetradecanoic acid and the photopolymerizable diacetylene molecule 10,12-pentacosadiynoic acid were prepared at the air water interface and transferred onto solid supports via Langmuir-Blodgett (LB) deposition. The addition of the perfluoroacid to the diacetylene surfactant results in enhanced stabilization of the monolayer in comparison with the pure diacetylene alone, allowing film transfer onto a solid substrate without resorting to addition of cations in the subphase or photopolymerization prior to deposition. The resulting LB films consisted of well-defined phase-separated domains of the two film components, and the films were characterized by a combination of atomic force microscope (AFM) imaging and fluorescence emission microscopy both before and after photopolymerization into the highly emissive "red form" of the polydiacetylene. Photopolymerization of the monolayer films resulted in the formation of diacetylene bilayers, which were highly fluorescent, with the apparent rate of photopolymerization and the fluorescence emission of the films being largely unaffected by the presence of the perfluoroacid.