The synthesis of polystyrene (PS) by atom transfer radical polymerization using the Fe(0)/CuBr2 catalytic system in dimethylformamide is reported. The effects of temperature, ligand, initiator structure, and monomer to solvent ratio on the polymerization kinetics are evaluated. PS with high molecular weight, low polydispersity, and telechelic structure are achieved and successfully used for further reinitiation or the copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition click reaction between alkyne- and azide-terminated PS. For the first time, suitable styrene polymerization rates are achieved using this cost-effective and environmentally attractive catalytic system. This method can be very useful in macromolecular engineering to afford PS-based materials with well-controlled structure. A cost-effective and environmentally attractive Fe(0)/CuBr2 catalytic system is used for atom transfer radical polymerization of styrene at, for the first time, suitable polymerization rates. The obtained polystyrenes (PS) have narrow molecular weight distributions and controlled telechelic structure, which can be used for further reinitiation and functionalization reactions, and, therefore, can be of great interest in PS-based macromolecular engineering. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.