Poly(N-isopropylacrylamide)(PNIPAM) with terminal aromatic groups were synthesized by atom transfer radical polymerization (ATRP), using N-isopropylacrylamide as monomer and phenyl 2-chloropropionate, (4’-phenyl)phenyl 2-chloropropionate and (2’,6’-diphenyl)phenyl 2-chloropropionate as initators. Then novel functional complexes of poly(N-isopropylacrylamide) and Eu(III) (PNIPAM-Eu(III)) with thermosensitive and fluorescent properties were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. Eu(III) was bonded to nitrogen and oxygen atoms in the polymer chain of PNIPAM and formed the complexes of PNIPAM-Eu(III). The lower critical solution temperatures (LCSTs) of PNIPAM-Eu(III) were slightly greater compared with that of PNIPAM. Europium(III) complexes had excellent fluorescence performance, the fluorescence spectrum present characteristic emission of Europium(III) at 613 nm.