Nanostructured Gd2O3:Eu3+ and Li+ doped Gd2O3:Eu3+ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li+ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li+ doped Gd2O3:Eu3+ thin films on annealing. AFM images of Li+ doped Gd2O3:Eu3+ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd-2 xEuxO3 (x = 0.10) and Gd-2 (x) yEuxLiyO3 (x = 0.10, y = 0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li+ doping is solely due to the increase in oxygen vacancies and the flux effect of Li+ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li+ doped Gd2O3:Eu3+ films at high temperature region is discussed in terms of increased Eu-O bond length as a result of Li+ doping. (C) 2009 Elsevier B. V. All rights reserved.