SiO2-PVA and Er3+-doped SiO2-PVA solution have been successfully prepared via sol-gel method. The main solution was transparent indicating the homogeneous mixture of SiO2 and PVA components. Thin film and nanofiber layer were fabricated using spin coating and electrospinning technique, respectively. Effect of the SiO2: PVA weight ratio was investigated to control the optical properties of the sample as well as the fibers diameter and their morphological appearance. The average diameter of the fiber varied from 79.41 to 122.20 nm depends on the SiO2: PVA weight ratio. It was found that electrospinning of the low viscosity of the solution leads to the formation of fiber with beads-on-string morphology. The weight ratio of SiO2: PVA (1:9) provides adequate chain entanglement as it produced dense fiber collection with fewer defects. All the samples are fully transparent in the VIS and NIR region, as evidenced by the percentage of transmittance with the range from 76% to 88%. Photoluminescence study shows that Er3+-doped SiO2-PVA nanofibers exhibit maximum red emission intensity at 0.4 wt. % of Er3+ doping. Er3+ doping did not significantly affect the diameter of the nanofibers due to relatively low concentration