A photochemical, alternative and eco-compatible approach to perfluoroalkyl derivatives of pyrene ispresented. The perfluoroalkyl chain is regiospecifically introduced at the 1 position of pyrene. Thesynthesized products have been embedded in a polymethylmethacrylate matrix by photocuring at 365nm. Both the photochemical reactions can be considered a “green tool” for the synthetic chemist inorder to obtain materials with prospective optoelectronic applications. The so-obtained composites havebeen the object of a study by UV and fluorescence spectroscopy in order to explore their luminescenceproperties. The small angle X-ray scattering and the transmission electron microscopy techniques wereused to investigate the microstructure. A correlation between the optical and the structural properties isherein presented.