The reactions of FeCl(dppe)Cp* and Ru(C⋮CC⋮CH)L2Cp‘ with Na[BPh4] and 1,8-diazabicyclo[5.4.0]undec-7-ene (dbu; 2 equiv) in a mixed thf/NEt3 solvent afford {Cp*(dppe)Fe}(C⋮CC⋮C){Ru(PP)Cp‘} (PP = dppe, Cp‘ = Cp*, 7; PP = (PPh3)2, Cp‘ = Cp, 8). Cyclic voltammetry shows that these mixed Fe/Ru complexes undergo sequential loss of up to three electrons, with the mono- and dioxidized species being isolated following chemical oxidation. Computational (DFT) and spectroscopic (IR, NMR, ESR, Mössbauer) studies are consistent with a polarized ground-state structure with oxidation leading to the gradual evolution of cumulenic character in the FeC4Ru moiety and a greater degree of orbital mixing between the Fe, C, and Ru centers than found in the related heterometallic complex [{Cp*(dppe)Fe}(C⋮CC⋮C){Re(NO)(PPh3)Cp*}]n+ ([6]n+). In contrast to the two-electron oxidation products derived from the diiron complex {Cp*(dppe)Fe}(C⋮CC⋮C){Fe(dppe)Cp*} (1) and iron/rhenium complex 6, the dications [7]2+ and [8]2+ feature a dominant contribution from a singlet ground state. Thus, while 6 behaves in a manner closely related to 1, 7 and 8 are more closely related to {Cp(Ph3P)2Ru}(C⋮CC⋮C){Ru(PPh3)2Cp} (2) and {Cp*(dppe)Ru}(C⋮CC⋮C){Ru(dppe)Cp*} (3), clearly demonstrating the pronounced role that choice of metal as well as formal electron count can play in tuning the electronic and magnetic properties of this fascinating class of compound.