Using a polyaryletherketone bearing carboxyl groups (PEK) as macromolecular ligand, Tb3+ and Ce3+ as central coordination ions, 1,10-phenanthroline (Phen) as the second ligand, a kind of novel terbium-cerium coordination polymer (PEK-Tb3+0.5Ce3+0.5-Phen) was prepared. The structure of PEK-Tb3+0.5Ce3+0.5-Phen was investigated by ICP, FTIR and XRD. The results showed that Tb3+ and Ce3+ ions coordinated to both the polymer ligand PEK and the second ligand Phen, and rare earth ions homogeneously distributed in the polymer matrix. The fluorescence measurement indicated that PEK-Tb3+0.5Ce3+0.5-Phen can exhibit the characteristic emission of Tb3+. Furthermore, the emission intensity of PEK-Tb3+0.5Ce3+0.5-Phen at 546 nm, corresponding to the green color, was higher than that of PEK-Tb3+-Phen.