The concept of photoinduced electron transfer has been explored for the development of polymeric transducers for optical ion-detection devices. For this purpose, a series of N-(9-anthrylmethyl)monoaza-18-crown-6 substituted poly(methacrylate)s were prepared, which differ in the chemical nature of the backbone. The fluorescent signaling in these systems is based on disturbances, upon complexation of K⊕, in the competition between de-excitation pathways of fluorescence and photoinduced electron transfer. The sensitivity and the ultimate enhancement of the fluorescence of these materials upon complexation of K⊕ were found to be strongly influenced by the chemical structure of the polymer backbone.