In this study, we investigated the influence of Bi2O3 and WO3 on both structure and optical properties of 50ZnO:(49 - x)B2O3:1Bi2O3:xWO3; x = 1, 5, 10 glasses doped with 0.5 mol% Eu2O3. IR spectroscopy revealed the presence of trigonal BØ3 units connecting superstructural groups, [BØ2O]- metaborate groups, tetrahedral BØ4- units in superstructural groupings (Ø = bridging oxygen atom), borate triangles with nonbridging oxygen atoms, [WO4]2- tetrahedral, and octahedral WO6 species. Neutron diffraction experimental data were simulated by reverse Monte Carlo modeling. The atomic distances and coordination numbers were established, confirming the short-range order found by IR spectra. The synthesized glasses were characterized by red emission at 612 nm. All findings suggest that Eu3+ doped zinc borate glasses containing both WO3 and Bi2O3 have the potential to serve as a substitute for red phosphor with high color purity.