The layer-by-layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3-thiophene acetic acid (PTAA) and Tb3+ ion by dipping the substrates alternatively in polymer and Tb3+ ion aqueous solutions. UV-vis measurement revealed that the absorbance has linearity with the bilayer number from layer to layer and the X-ray photoelectron spectrum (XPS) confirmed the existence of Tb3+ ion. The pH of both the polymer and TbCl3 solutions influence the thickness dramatically while the concentration of the solutions is not so sensitive. The luminescent spectrum of the complex film shows the characteristic emission of Tb3+ ion as well as the ligand indicating the formation of the complex.