The effects of co-doping Eu3+ ions in Sm3+ embedded WO3–Na2O–MgO–TeO2 glasses have been explored. The XRD spectrum determines the amorphous nature of the prepared sample. The UV–Visible spectra show that the dominant absorption bands occur at 7F0 → 5L6 (393 nm) and 7F0 → 5D2 (463 nm) for Eu3+ doped glass and the dominant absorption band for Sm3+ ions doped glass arises at 6H5/2 → 6P3/2 (402 nm). The energy transfer from Sm3+ → Eu3+ (4G5/2 → 5D0) upon excitation at 402 nm has been verified using the theory proposed by Dexter and Forster. The Inokuti-Hirayama model suggests that the possible energy transfer is dipole–dipole in nature which happens in Sm3+/Eu3+ co-doped glasses. As the energy levels 4I13/2 of Sm3+ ions and 5D2 of Eu3+ ions are very close, the luminescence transition due to 4G5/2 → 6H5/2 occurs upon excitation at 463 nm in co-doped glasses. The CIE1931 chromaticity coordinates illustrate that the present co-doped glasses have a range of emission from orange to red. The chroma and hue of the emitted colours of the present co-doped glasses are also computed using CIELab and it shows a linear change from orange to red with the increasing Eu3+ ion concentration in the present co-doped glasses. The obtained results show that these glasses have potential to find applications in various fields like solar cells, solid state lighting, display devices etc.