Eu3+ doped Ba2MgWO6 (BMW) double-perovskite was successfully synthesized for the first time by the co-precipitation method. The synthesis procedure, crystal structure, as well as morphology of obtained samples are presented. Domination of the 5D0–7F1 magnetic–dipole over forced electric–dipole transitions in the emission spectra indicates that Eu3+ ions are located in the high symmetry site with inversion center. Only one emission line assigned to the 5D0–7F0 transition was observed, confirming that europium substituted for only one host cation site. The photoluminescence excitation (PLE) spectrum is dominated by a strong and broad band related to the O2− → Eu3+ and O2− → W6+ charge transfer. The decay of the emission from the 5D0 and 5D1 levels was investigated. The temperature-dependent emission spectra showed that the T0.5 is equal to 350 K. Extinguishing mechanisms of the Eu3+ luminescence in the studied host are discussed.
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