Na2Ba6(Si2O7)(SiO4)2:Eu2+ with Ba substitute by Mg or Zn were firstly reported. Structure of Na2Ba6(Si2O7)(SiO4)2 showed regular changes with introducing Mg and Zn. The Eu emissions at three cation sites varied regularly with increasing Mg and Zn. The PL mechanism was preferential occupancy of Eu2+ at different cation sites. The introduction of Mg and Zn improved the thermal stability of phosphors.