AbstractA series of neutral and oxidized π‐bridged biferrocenes (Fc—x—Fc) and biferrocenylenes (FC(—x—)2Fc) (x= —CH=CH—, —CH3,C=CCH3—) were prepared and their physical properties have been studied by means of Mössbauuer and cyclic voltammetry. The electrode reaction of these bridged ferrocene derivatives appears to involve a consecutive two‐step oxidation process. The results also show that the voltage difference between the first and second oxidaton potentials of the bridged biferrocenes was found to be largely exceeded that founded for the corresponding the bridged biferrocenylenes. The Mössbauer data show that the oxidation of doubly bridged Fc(—x—)2Fc with iodine, DDQ, and TCNQ given the corresponding dioxidized salts only and no stable mixed‐