Two soft polyetherurethanes with pyrene or anthracene fluorofore on the quaternary ammonium groups were synthesized and characterized. The properties of these polymers and the corresponding monomers were studied through fluorescence spectroscopy, and for the pyrene-polymer the quenching of fluorescence in film state by nitrobenzene used as efficient quencher was also performed. The fluorescence measurements suggested a hydrophilic environment for pyrene molecule in the polycation, where an increased excimer emission was evidenced. UV photolysis experiments performed with light of 365 nm on one synthesized model containing anthracene in DMF solution showed that the absorption maximum from 367 nm decreased gradually with irradiation time, as the [4+4] dimerization process of anthracene occurred. Since the above polymers can form flexible of elastomeric type, it should be possible to develop vapor-based chemical sensors for detection of some analytics.