The reaction of Hg(TePh)(2) with AgX (X = Cl, NO3) in the presence of PPh3 and PMePh2 in dimethylformamide (DMF) affords the cluster [Hg6Ag4(TePh)(16)] (1) at room temperature or [Hg6Ag4Te(TePh)(14)](2) (2) with heating. When Hg(TePh)(2) is reacted with [Co(PPh3)(2)Cl-2] or [Ni(PPh3)(2)Cl-2], the clusters [Hg8Te(PhTe)(12)Cl-4]Q [3; Q = [Co(DMF)(6)](2+) (3a), [Ni(DMF)(6)](2+) (3b)] are formed. The syntheses of 1 and 2 occur with the incorporation of Ag-I into the cluster, and the single-crystal analyses show that the two ternary clusters consist of Hg, Ag, and Te centers occupying well-defined positions. Compounds 3a and 3b do not show the incorporation of the metal into the cluster, but the Co-II and Ni-II salts provide the Cl atom to generate the anionic cluster 3 stabilized by the [Co(DMF)(6)](2+) or [Ni(DMF)(6)](2+) ion.