The formation of complexes between Fe-III or Fe-II and 2,2’-dipyridyl (bpy) in the molar ratio 1:1 which occurs in DMF solutions in the presence of Cl- ions has been investigated by cyclic voltammetry and controlled potential electrolysis. The iron(III) complex undergoes three stepwise quasi-reversible reductions. The first two monoelectronic steps are preceded by chemical reactions that involve a loss of a Cl- ligand or a DMF decoordination. The two reduced products [FeCl(bpy)] and [Fe(bpy)] slowly decompose in solution. The whole voltammetric behaviour and the determination of the stability constants between [FeCl2(bpy)], [Fe(bpy)(3)](2+), [FeCl](+) and bpy entities are presented and discussed.