The photopolymerization study of novel diacetylene-decorated platforms obtained by self-assembling of properly- functionalized monomers onto pre-existing silver nanoparticles is reported. For this purpose, differently-terminated diacetylenes of general formula X–(CH2)m–C≡C–C≡C–(CH2)8–COOH have been synthesized and tested. Qual- itative and quantitative evaluation of the blue polymer photogeneration, performed by means of spectroscopic techniques, is reported and discussed in order to select the best performing photoresponsive nanohybrids to be employed in sensoristics as well as in optoelectronic and biomedical applications.