This paper demonstrates a systematic study of the synthesis and characterization of the hybrid of Mg–Al layer double hydroxides (LDHs), poly(ε-caprolactone) (PCL), and terbium ions (Tb 3+ ). The hybrid LDH-g-PCL-Tb 3+ -1,10-phenanthroline (Phen) was prepared by the combination of ring opening polymerization (ROP), click chemistry, and coordination chemistry. First, LDHs with a molar ratio of Mg/Al=2 were prepared by the co-precipitation method, which was subsequently functionalized with (3-chloropropyl) trimethoxysilane in order to introduce azide groups through the reaction of chlorine with sodium azide. Meanwhile, the acetylene functionalized PCL was prepared by ROP of ε-CL, followed by esterification of the hydroxyl groups using succinic anhydride. The click reaction of alkyne-PCL and N 3 -LDHs successfully afforded LDH-g-PCL, which was coordinated with Tb 3+ ions in the presence of Phen. The structure and properties of the nanohybrids were investigated by FT-IR, XPS, EDS, SEM, and TGA analyses. The data indicate the coordination of Tb 3+ ions with LDH-g-PCL nanohybrids. The content of Tb 3+ ions in the LDH-g-PCL-Tb 3+ -Phen complex was calculated to be 8.7% (w/w). The LDH-g-PCL-Tb 3+ -Phen complexes showed four emission bands with high fluorescence intensity centered at 489nm ( 5 D 4 → 7 F 6 ), 546nm ( 5 D 4 → 7 F 5 ), 586nm ( 5 D 4 → 7 F 4 ) and 623nm ( 5 D 4 → 7 F 3 ) with excitation at 328nm ( 3 F 6 → 5 G 6 ). The stability of LDH-g-PCL-Tb 3+ -Phen complexes under UV irradiation was high, and no leaching effect was observed.