(50-x)Na 2O-50P 2O 2-xAgCI (x = 0 to 15 mol%) glasses in bulk form were synthesized using meltquenching technique. Thin films of these silver doped sodium phosphate glasses were deposited by thermal evaporation process. The influence of deposition of these glasses in thin film form and subsequent annealing at 600 °C on the structure and optical properties such as transmittance, reflectance, refractive index and band gap have been investigated in detail. X-ray diffraction studies of the as-deposited films show the films to be amorphous whereas annealed films show existence of orthorhombic and monoclinic phase of NaPO 3 along with crystalline cubic phase of AgCI in doped glasses. Structural investigations of these annealed films show unique morphologies (needle-like and granular) at nano-scale. Both as-fabricated and annealed films are poor reflectors but show high transmittance in the entire spectral region under consideration, which is a direct consequence of particle size effects. Indirect band gap narrowing and variation in refractive index upon annealing is consistent with nanostructural transformations in these samples. Copyright © 2009 American Scientific Publishers.