This works investigates the mechanistic features related to the reactions between Fe(II)Salen and several organic halides used as initiators in Atom Transfer Radical Polymerization, Within the time scale of cyclic voltammetry, a fast reaction is observed between electrogenerated Fe(II)Salen and either ethyl 2-bromoisobutyrate, carbon tetrachloride or 1-chloro-1-phenylethane. Since no catalytic current is observed in cyclic voltammetry in the presence of RX, no fast mediated reductive cleavage of RX into R- + X- occured. An intermediate [R..X..FeSalen] complex was formed which was either relatively stable (ethyl 2-bromoisobutyrate and 1-chloro-1-phenylethane) or underwent further reduction (CCl4). In the presence of styrene and at 110 degrees C, polymerization is observed and the polydispersity of the resulting polystyrene appears to depend on the Fe(III)Salen/Fe(II)Salen initial ratio, The role of both Fe Salen and Fe(II)Salen in the regulation of radical concentration provided a controlled character to the polymerization. (C) 2009 Elsevier B.V. All rights reserved.