The coupling of electron and proton transfers is currently under intense scrutiny. This Communication reports a new kind of proton-coupled electron transfer within a homodinuclear first-row transition-metal complex. The triply-bridged complex [Fe-III(mu-OPh)(mu(2)-mpdp)Fe-II(NH2Bn)] (1; mpdp(2-) = m-phenylenedipropionate) bearing a terminal aminobenzyl ligand can be reversibly deprotonated to the animate complex 2 whose core [Fe-II(mu-OPh)(mu(2)-mpdp)Fe-III(NHBn)] features an inversion of the iron valences. This observation is supported by a combination of UV-visible, H-1 NMR, and Mossbauer spectroscopic studies.