Three series of new Ni/Fe/S cluster complexes have been prepared and structurally characterized. One series of such complexes includes the linear type of (diphosphine)Ni-bridged double-butterfly Fe/S complexes [(mu-RS)(mu-S=CS)Fe-2-(CO)(6)](2)[Ni(diphosphine)] (1-6; R = Et, t-Bu, n-Bu, Ph; diphosphine = dppv, dppe, dppb), which were prepared by reactions of monoanions [(mu-RS)(mu-CO)Fe-2(CO)(6)](-) (generated in situ from Fe-3(CO)(12), Et3N, and RSH) with excess CS2, followed by treatment of the resulting monoanions [(mu-RS)(mu-S=CS)Fe-2(CO)(6)](-) with (diphosphine)NiCl2. The second series consists of the macrocyclic type of (diphosphine)Ni-bridged double-butterfly Fe/S complexes [mu-S(CH2)(4)S-mu][(mu-S=CS)Fe-2(CO)(6)](2)[Ni(diphosphine)] (7-9; diphosphine = dppv, dppe, dppb), which were produced by the reaction of dianion [{mu-S(CH2)(4)S-mu}{(mu-CO)Fe-2(CO)(6)}(2)](2-) (formed in situ from Fe-3(CO)(12), Et3N, and dithiol HS(CH2)(4)SH with excess CS2, followed by treatment of the resulting dianion [{mu-S(CH2)(4)S-mu}{(mu-S=CS)Fe-2-(CO)(6)}(2)](2-) with (diphosphine)NiCl2. However, more interestingly, when dithiol HS(CH2)(4)SH (used for the production of 7-9) was replaced by HS(CH2)(3)SH (a dithiol with a shorter carbon chain), the sequential reactions afforded another type of macrocyclic Ni/Fe/S complex, namely, the (diphosphine)Ni-bridged quadruple-butterfly Fe/S complexes [{mu-S(CH2)(3)S-mu} {(mu-S=CS)Fe-2(CO)(6)}(2)](2)[Ni(diphosphine)](2) (10-12; diphosphine = dppv, dppe, dppb). While a possible pathway for the production of the two types of novel metallomacrocycles 7-12 is suggested, all of the new complexes 1-12 were characterized by elemental analysis and spectroscopy and some of them by X-ray crystallography.