<p>Rare-earth-doped glasses are at the forefront of photonic applications due to their outstanding optical tunability, yet the challenge of achieving efficient white light emission through eco-friendly and cost-effective glass hosts has persisted. Here in the present investigation, (Ce³⁺, Dy³⁺) co-doped Li₂O + CaO + B₂O₃ glasses have been fabricated via the melt-quenching method and systematically studied to achieve white light emission. The structural studies by XRD and Raman demonstrate the amorphous nature of the prepared glasses. The physical properties of the glass matrix were significantly improved by the addition of Dy³⁺ ions, as demonstrated by a decrease in interionic distance, an increase in density from 2.72 to 2.80&#xa0;g/cm³ and refractive index from 1.615 to 1.6215. The UV-visible-NIR optical absorption spectra showed characteristic Dy³⁺ absorption bands, a significant rise in the indirect band gap from 2.79 to 2.86&#xa0;eV, and a drop in Urbach energy from 0.181 to 0.164&#xa0;eV, all of which suggested less structural disorder in the glass network. The PL analysis exhibits distinctive emissions under UV excitation, with dominating yellow (∼575&#xa0;nm) and blue (∼480&#xa0;nm) emission peaks, which get stronger as the concentration of Dy₂O₃ increases. This also demonstrates an efficient energy transfer (ET) between Ce³⁺ ions as sensitisers to Dy³⁺ ions as acceptors, supported by the fluorescence lifetime decay studies, which show the reduced lifetime ascribed to dipole–dipole interactions as outlined by the Inokuti–Hirayama model (S = 6). In essence, (Ce³⁺, Dy³⁺) co-doped glasses with a matrix of Li₂O + CaO + B₂O₃ exhibit effective white light emission under UV light exposure. Among the investigated glasses, the glass composition featuring 0.5&#xa0;mol% Ce³⁺ and 1.0&#xa0;mol% Dy³⁺ demonstrates exceptionally well-balanced chromaticity coordinates, leading to a suitable choice for white light-emitting device applications.</p>