Abstract New π-conjugated butadiynyl ligand FcC(CH3)2Fc′–C C–C C–Ph (L1) has been synthesized and its reaction with Co2(CO)8 has been studied. New clusters [FcC(CH3)2Fc′–C C–C C–Ph][Co2(CO)6]n [(1): n = 1; (2): n = 2] and [Fc–C C–C C–Ph][Co2(CO)6]n [(3): n = 1; (4): n = 2] were obtained by the reaction of ligands FcC(CH3)2Fc′–C C–C C–Ph (L1) and Fc–C C–C C–Ph (L2) with Co2(CO)8 respectively and the composition and structure of the clusters and ligands have been characterized by elemental analysis, FTIR, 1H and 13C NMR and MS. The crystal structures of compounds L1, L2, 2 and 4 have been determined by X-ray single crystal analysis.