The synthesis of an acetonitrile-ligated molybdenum chloride cluster has been accomplished by the reaction of (Bu(4)N)(2)Mo6Cl8(CF3SO3)(6) and KSH in ethanol, followed by the extraction of the resulting product with SbCl5 in acetonitrile. The cluster, [Mo6Cl8(CH3CN)(6)]-(SbCl6)(4) . 2EtOH (1), consists of an octahedral arrange ment of six molybdenum atoms with eight chlorine atoms bridging the faces of the octahedron. A single acetonitrile ligand completes the coordination environment of each molybdenum atom and is positioned perpendicular to each of the six faces of the Cl-8 cube.