D5d- and C5v-symmetric double-decker buckyferrocene Fe2(C60R10)Cp2 (R10 = Me5Ph5 and Me10) represents a new type of diiron complexes featuring conjugative connection of two ferrocene groups by a hoop-shaped [10]cyclophenacene. The compounds exhibit two-electron oxidation and two-electron reduction behavior, generating dicationic and dianionic species. The two iron atoms interact with each other through the pi-conjugation of the cyclophenacene, as revealed by differential pulse voltammetric analysis of the D5d Fe2(C60Me10)Cp2.