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The applicability of model polydiacetylenes (PDAs) in hydrogen ions sensitive optodes was tested. Nanofibers mats were electrospun using a mixture of polyvinyl chloride (PVC) and polycaprolactone (PCL) together with 10, 12‐tricosadiynoic acid (TCDA) or 10,12‐pentacosadiynoic acid (PCDA). After the polymerization the mats were applied in colorimetric and fluorimetric pH sensors. The PDAs were formed by photopolymerization with a UV lamp (254 nm), resulting in a change of mats color from white to dark blue. The morphology of both fiber mats is similar (SEM images), and the average diameters of fibers were estimated as equal to 228±73 and 248±61 nm for TCDA and PCDA, respectively. As the pH increases, the color of the fiber mat changes from blue to red and the process can be followed visually. The result obtained by computer image analysis showed a sigmoidal increase in the intensity of red and …