Highly pure SiO2 and SiO2 :RE nanoparticles were synthesized by the sol-gel method. The morphological, structural and optical properties of the nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD results indicate that all the samples studied were free from impurities. SEM/TEM results indicate that the samples were well dispersed. Surface characterization of the nanocrystals by Fourier transform infrared spectroscopy has been carried out and the structure of surface-bound SiO2 based on spectral analysis is proposed. Thermoluminescence (TL) characteristics were investigated to study the influence of rare earth dopants (Tb, Ce, Eu, Dy) on SiO2 matrix subjected to 0.5 kG (1 h) γ-irradiation. Among these rare earth elements, Eu(3+) was found to be the most efficient dopant for SiO2 showing maximum thermoluminescence intensity. SiO2 :Eu0.5 seems to be a promising candidate for use as a TL dosimeter.