In the wide panorama of diacetylenic lipids, the photoresponsive conjugated 1,3-diyne function is usually encased into the hydrocarbon chain of the amphiphile at a variable distance from the headgroup. Therefore, the polydiacetylene network obtained by polymerization upon UV irradiation of the corresponding liposomes, exploited as sensing function, is embedded in the hydrophobic region of liposomes. Structurally related cationic diacetylenic amphiphiles featuring the conjugated triple bonds proximate to charged nitrogen were synthesized and evaluated in their ability to polymerize under aggregative conditions. The occurrence of polymerization only in certain aggregating conditions was rationalized by nuclear magnetic resonance (NMR) and Langmuir trough experiments.