The use of surface-functionalised polymers has shown great potential for application, emphasising the development of flexible optoelectronic devices (FOD). There are several ways to carry out this functionalisation, attributing different characteristics to the resulting material. In the present study, polyethylene terephthalate (PET) films were surface functionalised with [4-(2-hydroxy naphthyl)diazenyl] benzoic acid using UV radiation and direct grafting method. The resulting films were characterised using different techniques, which enabled the identification of functional groups characteristic of the compound azo, thus proving that both methods used for surface functionalisation were efficient. Subsequently, the sensing capabilities of these films was evaluated by being exposed to solutions of different cations. The fluorescence signal was the measurable response, in which its variation is dependent on the interaction of analytes with the functionalised surface of the PET film. The main advantages observed in this study are simplicity, low cost and the possibility of using recycled polymer, contributing to sustainable development and environmental conservation.