The optical and structural properties of 50P(2)O(5):50BaO glasses prepared by melting have been investigated for additive concentrations of 10 and 1 mol% of CuO and SnO dopants. Absorption and photoluminescence spectroscopies were employed in the optical characterization, whereas structural properties were assessed by P-31 nuclear magnetic resonance (NMR) spectroscopy. Residual Cu2+ was detectable by absorption spectroscopy for the highest concentration of CuO and SnO. More prominently, the optical data suggests contributions from both twofold-coordinated Sn centers and Cu+ ions to light absorption and emission in the glasses. The luminescence depends strongly on excitation wavelength for the highest concentration of dopants where a blue-white emission is observed under short-wavelength excitation (e.g., 260 nm) largely due to tin, while an orange luminescence is exhibited for longer excitation wavelengths (e.g., 360 nm) essentially due to Cu+ ions. On the other hand, dissimilar luminescent properties were observed in connection to Cu+ ions for the lowest concentration studied, as the copper ions were preferentially excited in a narrower range at shorter wavelengths near tin centers absorption. The structural analyses revealed the glass matrix to be composed essentially of Q(2) (two bridging oxygens) and Q(1) (one bridging oxygen) phosphate tetrahedra. A slight increase in the Q(1)/Q(2) ratio reflected upon SnO doping alone suggests a major incorporation of tin into the glass network via P-O-Sn bonds, compatible with the 2-coordinated state attributed to the luminescent Sn centers. However, a significant increase in the Q(1)/Q(2) ratio was indicated with the incorporation of copper at the highest concentration, consistent with a key role of the metal ions as network modifiers. Thus, the change in Cu+ optical properties concurs with different distributions of local environments around the ions induced by variation in metal ion concentration. Luminescence decay curve analyses were found in agreement with the presence of Cu+ ions in the glasses suggesting their existence in tetragonally-distorted octahedral sites. (C) 2014 Elsevier B.V. All rights reserved.