Processes of ballistic and hot electron relaxation in extended bulk as well as nanostructured silica have been analyzed by means of a phonon-based scattering model and respective Monte-Carlo computer simulation. Optical as well as acoustic phonons are taken into account. Trajectories of electrons and their energy attenuation in nanostructured silica are additionally affected by scattering processes at the grain boundaries between the nanoparticles, i.e. by surface phonon as well as potential scattering. Moreover, a flatter conduction band and a higher effective electron mass have been taken into account too. According to these calculations, electrons with an initial energy of several eV, but still below the valence band ionization threshold, were thermalized in 50–300fs increasing with the silica grain size from 1nm up to bulk material. The electron emission probabilities over the surface barrier into vacuum are extended up to depths of 60–100nm, respectively, increasing with enhancement by an electric field.