Abstract: A series of polymer complexes of Eu-Tb with α-thenoyltrifluoroacetone(HTTA) and 5-sulfoalieylic acid(SSAH₂) as micro molecule ligand and copolymer of acrylic acid and methylmethacrylate as polymer ligand was synthesized. The complexes were characterized by means of elemental analysis, ultraviolet and infrared spectroscopies. Their fluorescence properties and the mutual effect on the fluorescence properties of europium and terbium were investigated Via the fluorescence spectroscopy. The fluorescent emission peak location and the relationships between the fluorescent emission intensity and composition were also discussed. The results show that the fluorescent intensity has a sensitize or quench effect between Eu³⁺ and Tb³⁺ in the rare-earth(Eu,Tb) polynuclear polymer fluorescence complexes. Eu³⁺ ions shows a strong luminescence quenching effect on Tb³⁺ ions, and this effect is the strongest when the n(Eu³⁺):n(Tb³⁺) is 1:1. When Tb³⁺ ion concentration is low (n(Eu³⁺):n(Tb³⁺) is greater than 1:1), Tb³⁺ ions exhibit a luminescence quenching effect on Eu³⁺ ions; when Tb³⁺ ion concentration is high(n(Eu³⁺):n(Tb³⁺) is less than 1:1), Tb³⁺ ions display a very strong sensitization effect on Eu³⁺ ions.