Reaction of [MoOS3](2-) and [WS4](2-) with Cudtp (dtp = diethyl dithiophosphate) gave rise to the clusters [Bu4N](2)[{MoOS3}(4)Cu-12(dtP)(6)], 1, and [Et4N][{WS4Cu4}(dtp)(3)], 2, respectively. In cluster 1, the dtp(-) ligands act as both monodentate and bidentate ligands that bridge between Cu atoms and link together a closed double-cubane-like [Mo2O2S6Cu6](2+) core and two incomplete cubane-like [MoOS3Cu3](+) units. In cluster 2, the [WS4Cu4](2+) fragments were connected via bidentate and doubly bridging dtp- bridges to give a chain polymeric anion. Cluster 1 is the first example of a Mo/Cu/S cluster that contains a closed double-cubane-like structure. Compound 2 is also rare and the first W/Cu/S polymer with dtp(-) linkages.