A series of SiO2 nanostructures codoped with Eu3+; Mg2+ ions were obtained by a sol-gel method. The gels synthesized by the hydrolysis of Si(OC2H5)4, Eu(NO3)3·6H2O, and Mg(NO3)2 were heated in air at 600°C for 2 hours. Firstly, the total amount of Eu3+ ions was varied from 0 to 2.0 mol% to investigate the effect of self-damping, while in the second case, the Eu3+ ions were kept constant in the experiment at 0.5 mol% total doping and Mg2+ ions varied. The samples were characterized by X-ray diffraction, TEM, EDS, and UV lamp-excited luminescence spectroscopy. The Eu3+ ions were homogeneously dispersed in the silica and interacting with the small (1–5 nm) amorphous silica matrix. Strong red emissions located at 614 nm and 590 nm for doped and codoped SiO2 were observed from the UV light excitation at room temperature. The composition of around 1.25 mol% Eu3+ gave highest emission intensity. SiO2; Mg2+ ions portray strongly enhanced emissions due to energy transfer from Mg2+ to Eu3+, which is due to radiative recombination. An increase in luminescence intensity was observed as the Mg2+-to-Eu3+ ratio increased for the range investigated. The results show Eu3+ ion is located inside or at the surface of disordered SiO2 nanoparticles.