A ligand (H2L) containing linear N4O2 coordination sites was synthesized, and its chemical structure was confirmed by infrared spectroscopy and nuclear magnetic resonance spectroscopy. Its binary Tb(Ⅲ) complex having macrocycle structure and ternary complex with 2,2'-bipyridine as the second ligand were prepared. And their structures and luminescent properties were investigated by IR, TG-DTA and fluorescence spectra. The results showed that the complexes emit strong characteristic fluorescence of Tb(Ⅲ) under UV excitation, the ligand is an excellent sensitizer to Tb(Ⅲ), and the fluorescence intensity of the ternary complex is significantly greater than that of the binary complex.