The synthesis of the cluster complexes [(Cp’’’Co)3(μ3,η2:η2:η2-E3)(μ3-E)] (E=P (3), As (4)) starting from the anionic triple-decker complexes [K(18cr6)(dme)2][(Cp’’’Co)2(μ,η4:η4-E4)] (E=P (1), As (2)) by electrophilic quenching with the Co dimer [(Cp’’’CoCl)2] is reported. Both complexes show a distinct redox chemistry, which was first investigated by cyclic voltammetry. Subsequently, the monoanions [K(L)(sol)n][(Cp’’’Co)3(μ3,η2:η2:η2-E3)(μ3-E)] (E=P, L=18cr6, sol=dme, n=2 (5), E=As, L=2,2,2-crypt, n=0 (6)), the monocations [(Cp’’’Co)3(μ3,η2:η2:η2-E3)(μ3-E)][FAl] (E=P (7), As (8)) and the dications [(Cp’’’Co)3(μ3,η3:η3:η3-E4)][TEF]2 (E=P (9), As (10)) could be realized experimentally and isolated in moderate to good yields. All compounds were characterized by single crystal X-ray structure analysis, NMR and EPR spectroscopy, mass spectrometry and elemental analysis.