We report the effect of 80keV Xe+ ion irradiation on the morphological and optical responses of TiO2 nanoparticles spread over commercially available polytetrafluoroethylene (PTFE, Teflon). These nanoparticles were synthesized via a convenient, sol–gel approach with titanium isopropoxide as the main precursor. From X-ray diffraction (XRD) studies we found that, the nanoparticles crystallize in anatase phase and with a preferential orientation of crystallites along (101) plane. Upon irradiation at a fluence of 1.25×1017ions/cm2, the nanoparticle dimension was found to increase from a value of ∼9nm to ∼20–30nm. Essentially, particle growth is predicted as a consequence of swelling behavior accompanied by the formation of Xe van der Waal crystals in isolated regions of nano-titania. Evidence of nanoripples was also witnessed on the surface of the irradiated nano-titania. The morphological evolution was assessed both by atomic force and transmission electron microscopies (AFM and TEM) independently. From the UV–Vis optical absorption studies, the estimated optical band gap was found to drop with increasing fluence, while refractive index exhibited a remarkable improvement. Photoluminescence (PL) studies have revealed that, the band edge emission and those due to the self trapped excitons (STE) and other oxygen vacancy related ones were manifested considerably as a result of Xe ion irradiation.