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Polarographic half-wave potentials for two reduction steps of 49 cyclopentadienyliron complexes of substituted arenes or heterocycles in dimethylformamide were determined. A fast cyclic voltammetry (10–40 V/s) was used to study the electron transfer kinetics of some of these complexes. After correction for the double layer effects, the rate constants of all the complexes studied show that the transfer of electrons in the second reduction step occurs significantly faster than in the first one. This was interpreted as a result of greater delocalization of electrons in the 20-electron complexes of iron compared to the 19-electron complexes.