A bis-double-decker complex has been assembled from the nickel bisdithiolene complex [Ni(S2C2Me2)(2)](1-/2-) and two [Cp*Fe](+) units (Cp* = C5Me5). The complex, [(eta(5)-Cp*-Fe-mu-eta(5),eta(5)-((S2C2Me2)(2)Ni)Fe-eta(5)-Cp*](n) (1(n)), was isolated in two charge states (n = 0, 1). The structure of 1(+) was confirmed by X-ray crystallography for 1(+) PF6- and 1(+) BF4-and it shows the nickel bisdithiolene units pi-donating to iron centers. Both salts crystallize in a centrosymmetric space group (center of inversion at nickel). Computational (density functional theory) data indicate a highly delocalized spin density for 1(+) The reaction of 1 with 1 or 2 equiv of HBF4 leads to oxidation to form 1(+) or 1(2+), respectively. On an electrochemical time scale, reversibility is observed for the redox series 1/1(+)/1(2+) with an additional slower step for oxidation of 1(2+).