Rare earth metal ions containing polymer ternary complexes were synthesized and characterized. The functional polymers investigated were polymer-bond triphenylphosphine (PBDP), polymer-bond triphenylarsine (PBDAs), polymer-bond triphenylstibine (PBDSb), and polymer-bond triphenylbismuthine (PBDBi) as polymer ligands. Several substances, such as thenoyltrifluoroacetone (TTA), and 8-hydroxyquinoline (oxin), phenanthroline (phen) were used as low molecular weight ligands. The results show that TTA is the best low molecular weight ligand among them. The fluorescence properties of synthesized complexes were investigated; PBDAs is a better polymer ternary complex that possesses stronger fluorescence intensity coordinated with any low molecular weight ligand. The fluorescence Lifetimes of Eu3+-containing polymer ternary complexes are between 0.350 and 0.469 MS. The reaction conditions of the formation and stability of rare earth metal ions-polymer-TTA ternary complexes are discussed.