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New ternary Eu(III) 5-(2-pyridyl-1-oxide)tetrazolate complexes with phosphine oxide co-ligands have been synthesized and characterized by elemental analysis, and IR and 1H NMR spectroscopic techniques. The analytical data revealed that these complexes are mononuclear, and the central Eu(III) ion is coordinated by three oxygen and three nitrogen atoms of the tetrazolate and two oxygen atoms from the phosphine oxide ligands. The ancillary ligands increased remarkably the luminescence efficiency of the Eu(III) tetrazolate.