Amorphous fluorinated optical polymers, characterized by high transparency in the visible and near infrared spectra, high glass transition temperature and very good resistance to chemical environment, have been developed by co-polymerisation of tetrafluoroethylene (TFE) and 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole (TTD). In this work we study at molecular level the effect of the introduction of the bulky TTD unit in a perfluoroalkyl chain. In particular the effect on the molecular structure and chain flexibility is investigated and spectroscopic markers correlated to chemical and structural defects are identified. The study includes a thorough experimental spectroscopic analysis (infrared and Raman spectra) of several different copolymer samples and a modelling based on Density Functional Theory calculations and semiempirical calculations on suitable model molecules. (c) 2008 Elsevier Ltd. All rights reserved.