Abstract: Chloromethylated Polystyrene (CMPS) was first prepared with 1,4-bis (chloromethoxy) butane (BCMB) as the chloromethylation reagent. Then nucleophilic substitution between CMPS and phydroxybenzaldehyde(HBA) was conducted,resulting in benzaldehyde(BA) modified polystyrene(PS-BA) on its side chain. Finally,a reaction between 3-aminopyridine(AP) and the aldehyde group of PS-BA was allowed to form Schiff base functionalized polystyrene PS-SB. The chemical structure of PS-SB was characterized by FTIR and ¹H NMR spectra. PS-SB as the first ligand and phenanthroline (Phen) as the second ligand,binary and ternary polymer-rare earth complexes,PS-(SB)₃-Eu(Ⅲ) and PS-(SB)₃-Eu(Ⅲ)-(Phen),were prepared,respectively. The florescence emission properties of the two complexes were preliminarily explored. The experimental results show that the rate of the nucleophilic substitution reaction between CMPS and HBA has a mechanism of S_N 1. For the nucleophilic substitution reaction,N,Ndimethylacetamide(DMAC) with stronger polarity is a suitable solvent,and the temperature of 80℃ is appropriate. The macromolecular ligand PS-SB can produce obvious sensitization for the fluorescence emission of Eu(Ⅲ) ion,and both the binary and ternary complexes emit stronger characteristic fluorescence of Eu(Ⅲ) ion.