The use of microfluidics technology and the miniaturization of analytical techniques is of high interest for the chemical and nuclear industries. In the latter, the reduction of effluents deriving from actinides concentration monitoring along R&D and pilot-scale purification processes is a permanent concern. Indeed, the extremely harsh operation conditions limit the implementation of standard analytical techniques and methodologies, and in this regard, the use of spectrophotometric techniques for effluents characterization becomes advantageous in terms of robustness, implementation and sensitivity at the microfluidic scale. In this work, we report a study of the effect of exposure to different chemicals used in hydrometallurgical processes, and to gamma radiation typical of the Plutonium and Uranium Refining by Extraction process, on the optical and structural properties of different polymeric materials commonly used for the fabrication of microfluidic and optofluidic systems. This study shows that low-cost castable and/or engravable materials (e.g. polydimethylsiloxane and poly-methyl methacrylate) are ideal for the study and development of Photonic Lab on a Chip systems that will be used in a nuclear environment.