The synthesis, characterization, and functionalization of polydiacetylene (PDA) networks on solid substrates is presented. A highly transparent and cross-linked diacetylene film of DCDDA-bis-BA on a solid substrate is prepared first by tailoring the monomers with organoboronic acid moieties as pendant side groups and consequent drop-casting and dehydration steps. Precisely controlled thermal curing plays a key role to obtain properly aligned diacetylene monomers that are closely packed between the boronic acid derived anhydride structures. A second cross-linking, which occurs by polymerization of the diacetylene monomers with UV irradiation, induces a transparent to blue color shift. Accordingly, colored image patterns are readily available by polymerization through a photomask. The color change that takes place as a response to various organic solvents can be simply detected by naked eyes. The thermofluorescence change of PDA networks is demonstrated to be an effective method by which to obtain the microscale temperature distribution of thermal systems. The ease of film formation and stress-induced blue-to-red color change with a simultaneous fluorescence generation features of the network structure should find a great utility in a wide range of chemical and thermal sensing platforms.