In this work, Fe(0)-mediated single electron-living radical copolymerization of styrene (St) and acrylamide (AM) was investigated at ambient temperature in N,N-dimethylformamide using carbon tetrachloride as initiator and tetramethylethylenediamine as ligand. Kinetic studies showed that the copolymerization followed the first-order kinetics model. The resulting copolymers of St and AM possessed predetermined molecular weights and narrow molecular weight distribution, which agreed with the character of controlled/living polymerization. On the basis of Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (NMR), the monomer reactivity ratios were calculated. The amount of ligand played an important role in copolymerization. The obtained polymer was characterized by FTIR, 1H NMR, 13C NMR, and gel permeation chromatography. The living characteristics were demonstrated by chain extension experiment. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2919-2924