Current activity in the chemistry of Polyoxometalates (POM) is widely driven by potential applications in catalysis, magnetism, materials sciences and in Biology. During the last fifteen years, we used the dimolybdic complex [Mo2O2S2]2+ as precursor or as linker to build new families of polyoxo(thio)metalates (POTM) compounds exhibiting a large variety of size, charges and properties. In this contribution, we will give an overview of the supramolecular systems based on this fragment, from coordination complexes, to cyclic systems resulting from the self-condensation of some [Mo2O2S2]2+ units and finally to giant supramolecular systems based on the combinations of this unit with molybdates or tungstates.[1,2] A particular attention will be paid on the experimental conditions used for the preparation of these systems, their characterizations in solution by various NMR techniques and their properties respectively in biology,[3] in electro-catalysis for the production of hydrogen [4] and in materials science [5].figure