The reactivity of Cp*4Sb4 (1) towards ionic compounds and transition metal complexes with labile ligands was investigated in order to synthesize polyantimony ligand complexes. The silver salts [Ag][X] and the metalate Na[Cp*Mo(CO)3] were primarily used, leading in the raction with Cp*4Sb4 to the formation of [Cp*2Sb][X] (X = TEF (2a), FAL (2b)), [(Cp*Mo(CO)3)3(μ3-Sb3)] (3) and [Cp*Mo(CO)2(η3-Sb3)] (4), respectively. The reaction of 1 with the transition metal complexes [(Cp'''M)2(tol)] leads to a degradation of the original Sb4 unit and to the formation of [(Cp'''M)4(μ3-Sb)4] (M = Ni (5); Co (6)). Towards [CpRFe(CO)2]2, substitutions on the antimony atoms were observed to give [{CpRFe(CO)2}4(μ4-Sb4)] (CpR = Cp'' (7a), Cp''' (7b)). All complexes were characterized by XRD and spectroscopic methods.