Four new ternary rare earth complexes RE(NTA)2AA (RE=Sm3+,Eu3+,Tb3+,Dy3+) have been synthesized by the reaction of rare earth chloride(RECl3·6H2O) with Acrylic Acid (HAA) and 4,4,4-trifluoro-1-(3-pyridyl)-1,3-butanedione(NTA) in alcohol. The copolymerization of the complexes RE(NTA)2AA (RE=Sm3+,Eu3+) with methyl methacrylate (MMA) has been studied by 2,2-azobis-isobutyronitrile as an initiator. Influence of adding Eu(Ⅲ) and 2,2′-bipyridine(bipy) into copolymer Eu(NTA)2AA-co-MMA on fluorescence property of the Eu copolymer was investigated. The compositions of the complexes and copolymer were characterized by means of elemental analysis and FTIR. The heat decomposing behaviors of the complexes were determined by TG-DTA. The glass transition temperature and molecular weight were obtained by DSC and GPC. The results of fluorescence properties show that the Eu,Sm complexes and Eu copolymer can efficiently emit fluorescence,but the Tb and Dy complexes only emit the fluorescence of β-diketone ligand.