Silica glasses co-doped with varying concentrations of Er3+ (0.8, 1.5, 4, and 8 mol %) were fabricated employing the sol-gel technique. The effects of erbium concentration were evaluated through several characterization techniques, including X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV-visible transmission spectroscopy, and photoluminescence analysis. The incorporation of erbium ions significantly altered the structural, optical, and photoluminescence properties of the doped glasses. XRD analysis revealed the presence of SiO2 in both tetragonal and hexagonal forms, along with Er2SiO5 crystalline phases. SEM images showed irregular rod-shaped structures with agglomeration and micro-flake cubic shapes. FTIR spectroscopy provided insights into the structural characteristics of the materials. Notably, the optical band gap energy of the glassy films increased, accompanied by fluctuating Urbach energy and a slight reduction in the refractive index, attributed to structural changes within the glass network. Photoluminescence spectra indicated strong emissions at 523 and 543 nm, corresponding to the transitions 2H11/2 → 4I15/2 and 4S3/2 → 4I15/2, respectively. Additionally, a notable near-infrared emission at 1532 nm was observed, linked to the transition 4I13/2 → 4I15/2. The color coordinates of the produced glasses were found to be near the green or yellow regions, suggesting potential applications in optical amplifiers, lasers, and low-emissivity coatings.