The first discrete hexanuclear metal clusters with cores adopting the M6(μ-O)12 cubo-octahedral topology have been synthesized in the course of a simple one-pot reaction. We present a new class of rhenium clusters which are the first hexanuclear rhenium complexes with 12 bridging ligands and the first clusters with octahedrally arranged Re atoms bridged only by O atoms forming a unique cube-like Re6(μ-O)12 unit. Our synthetic strategy demonstrates a new approach to the syntheses of polynuclear rhenium complexes under mild conditions. We discovered that the [Re6(μ-O)12(3-Mepy)6]BPh4 cluster compound has the ability to undergo reversible or/and quasireversible redox reactions without changing spatial structure and overall geometry. Subsequently, a reduction reaction of [Re6(μ-O)12(3-Mepy)6]BPh4 was performed successfully and almost quantitatively resulting in the formation of the molecular [Re6(μ-O)12(3-Mepy)6] complex.