In order to achieve the target synthesis of Eu(III) cross multiligand complexes with the designated coordination mode, the precursor compound was prepared by synthesis of rare earth nitrates, -naphacyltrifluoroacetonate (NTA) and diphenyl sulfoxide (DBSO) ligands, then the coordination of carboxyl group with Eu(III) ions was achieved by replacing the NO3- in precursor compound with p-methoxybenzoic acid (POBA). Owing to the larger steric resistance coordination from the ligands of -naphacyltrifluoroacetonate and diphenyl sulfoxide in precursor compound, the target synthesis of the bidentate chelating coordination of carboxylate groups with Eu(III) ions was achieved. The complexes related were characterized by elemental analysis, infrared spectroscopy, scanning electron microscopy, fluorescence spectroscopy, and thermogravimetry, furthermore based on the characterization results speculated the chemical structures. The results showed that bidentate chelate complex Eu(NTA)2(POBA)(DBSO)2 had better dispersion properties and higher efficiency of energy transfer than mixed coordination complex Eu(POBA)(NTA)2(DBSO)2, the main emission band of bidentate chelate complex becomed sharper and the split peak of the main emission was weaker than that of mixed coordination complex, and mixed coordination complex Eu(POBA)(NTA)2(DBSO)2 had slightly better thermal stability than that of bidentate chelating complex Eu(NTA)2(POBA)(DBSO)2. Two bright red fluorescent material were obtained.