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In the course of preparing Mn‐doped phosphors, the mix‐valence state of Mnn+ ions may be obtained with associated interesting properties. This work prepared a new phosphor Ba3MgSb2O9:Mn (BMS:Mn) by a traditional high‐temperature solid‐state synthesis method. In this structure, Mnn+ can replace Mg2+ site as Mn2+ oxidation state or Sb5+ site as Mn4+. Moreover, the emitting bands of Mn2+ and Mn4+ at...