Polytetrafluoroethylene (PTFE) polymer samples were irradiated by 50 MeV Li 3+ ion beams to the fluences of 1 × 10 10 , 1 × 10 11 , and 1 × 10 12 ions/cm 2 . The structural, optical, and chemical properties were studied by X-ray diffraction (XRD), UV-visible (UV-vis) spectroscopy, and Fourier transform infrared (FTIR) spectroscopy, respectively. The XRD analyses showed amorphization of the polymer sample at fluences of 1 × 10 10 and 1 × 10 11 ions/cm 2 . Crystallite size (calculated by applying the Scherrer formula) decreased for irradiated samples at fluences of 1 × 10 10 and 1 × 10 11 ions/cm 2 . The other factors like microstrain (ε), dislocation density (δ), and distortion parameters (g) showed variations at these fluences. However, there was no change in the interchain separation (R) and interplanar distance (d) for all irradiated samples. UV-vis showed a shift of the absorption edge of irradiated samples towards the visible region. The band gap energy (E g ) was calculated using Tauc's relation, and its value decreased with an increase of ion fluence for all irradiated samples. The number of carbon atoms per conjugation length (N) increased for the irradiated samples. The FTIR results revealed the liberation of CF 2 groups and the appearance of some new bands after irradiation. C