Rhenium-molybdenum cluster compounds K5.3Rb0.7[Re3Mo3S8(CN)5] (1) and K4.4Cs1.6[Re3Mo3S8(CN)5] (2) are obtained by the interaction of an equimolar mixture of ReS2 and MoS2 with molten KCN and RbI/CsCl, respectively. The structure of the complexes is determined by the XRD method. The compounds crystallize in the tetragonal crystal system, space group I4/m. The crystal structure is composed of anionic chains of [Re3Mo3S8(CN)4(CN)2/2]6– aligned along the a crystallographic axis and M+ cations located in voids of the lattice. The effect of additional Cs+ and Rb+ cations on the crystallographic parameters and geometric characteristics of the clusters is analyzed.