Poly (N-vinylacetamide) (PNVA) was synthesized by the free radical polymerization and its samarium (III) binary complex was prepared and characterized by means of IR, UV-vis, X-ray photoelectron spectroscopy (XPS) and fluorescence spectra. The fluorescent intensity of samarium (III) characteristic emission was increased significantly due to efficient energy transfer from polymeric ligand to Sm (III) ion in the complex.