The reactivity of Fe/S and Fe/Mo/S clusters, similar or analogous to those occurring in biological systems, with thiophilic metal ions has not been explored. In this Communication, we demonstrate that synthesis of heteropolynuclear clusters with different coordination geometries for different metals at different sites is possible by metal substitution or by metal addition reactions. The two clusters we report herein ([(Cl-4-cat)(2)Mo2Cu5Fe4S9((PPr3)-Pr-n)(7)(SPnPr(3))(2)]PF6 and [(Cl-4-cat)(2)Mo2Cu6Fe4S10(PnPr(3))(6)]) contain Fe, Mo, and Cu, which display pseudotetrahedral, pseudooctahedral, and pseudotrigonal geometries, respectively. The synthesis of these clusters is achieved by the addition of appropriate amounts of [Cu(CH3CN)(4)](+) to [(Cl-4-cat)(2)Mo2Fe8((PPr3)-Pr-n)(6)]. The formation of the different products is temperature- and solvent-dependent. The Cui units incorporated into the metal cluster framework, either bind to available lone pairs of the already bridging S ligands or displace the less thiophilic Fe atoms. Among the essential features of these new molecules are recognizable Fe/S fragments including an Fe6S9 core in the first cluster and the pentlandite Fe4Cu4S6 core in the second cluster.