Abstract: Firstly, the Schiff-base reaction occurred between polysulfone(PSF) modified with hydroxybenzaldehyde (BA) and aminopyrazine (AP), leading to the aminopyrazine type bidentate Schiff base(APSB) ligand-functionalized PSF, APSB-PSF. The chemical structure of APSB-PSF was fully characterized by FT-IR and ¹H-NMR spectra. Subsequently, APSB-PSF as macromolecular ligand and 1,10-phenanthroline (Phen) as small molecular and the second ligand, were coordinated to Tb(Ⅲ) ion, obtaining the binary polymer-rare earth complex Tb(Ⅲ)-(APSB)₃-PSF and ternary complex (Phen)₁-Tb(Ⅲ)-(APSB)₃-PSF, respectively. The fluorescence-emission properties and luminescence mechanism of these complexes were studied. The experimental results show that the ligand APSB-PSF can not only absorb ultraviolet light strongly, but also emit strong fluorescence by itself. However, after coordinated to Tb(Ⅲ) ion, the absorption intensity of APSB-PSF is essentially the same, but its fluorescence emission is reduced greatly, that is, energy transfer intramolecularly occurred. At the same time, the complex Tb(Ⅲ)-(APSB)₃-PSF emits stronger characteristic fluorescence of Tb(Ⅲ) ion than TbCl₃, due to accepting the transferred energy from APSB-PSF, namely the sensitization effect of APSB-PSF on the luminescence of Tb (Ⅲ) ions was occurred. The triplet state energy of the bonded ligand APSB is not matched with the resonant energy level of Eu(Ⅲ) ion, resulting in that the complex Eu(Ⅲ)-(APSB)₃-PSF hardly emits fluorescence. In addition, the ternary complex (Phen)₁-Tb(Ⅲ)-(APSB)₃-PSF also emits the characteristic fluorescence of Tb(Ⅲ) ion, and its fluorescence emission intensity is higher than that of the binary complex Tb(Ⅲ)-(APSB)₃-PSF.