Erbium-doped silica films were synthesized using a two-step sol–gel methodology that involved acid and base catalysts, with erbium concentration ranging from 0.2% to 6% and annealing temperatures varying from 500 °C to 900 °C. The photoluminescence spectra showed that the samples exhibiting efficient emission were annealed at 800 °C and 900 °C and doped with 3% and 6% erbium. The X-ray diffraction analysis revealed that the internal structure of the films was influenced by the different annealing temperatures and the doping concentrations. Samples with dominant 4f transitions were modelled. The results suggest that the proposed method is a promising approach for the synthesis of erbium-doped silica films with potential applications in optical devices.