The conditions and features of the formation of Langmuir monolayers of symmetrical and asymmetrical diacetylene N-arylcarbamates and the structural organization of Langmuir-Schaefer films based on them were studied. Photopolymerization of monolayer solid films of two types of molecules was monitored using absorption spectroscopy and showed the transition of diyne molecules to the blue phase polydiacetylene state. The efficiency of the solid-phase topochemical polymerization reaction in a film of symmetrical diynes turned out to be 5 times higher than in a film of asymmetrical diyne molecules. The morphology of monolayer surfaces before and after UV irradiation was studied using scanning electron microscopy.