A series of heterometallic Pt-M (M = Zn and Cd) sulfide aggregates with growing nuclearities {Pt2M}, {Pt4M}, and {Pt4M2}, viz., [ZnPt2Cl2(PPh3)(4)(mu(3)-S)(2)] (2), [CdPt2Cl2(PPh3)(4)(mu(3)-S)(2)] (3), [Pt-2(PPh3)(4)(mu(3)-S)(2)](2)[ZnSO4](2) (4), [Pt-2(PPh3)(4)(mu(3)-S)(2)](2)[CdSO4](2).H2O (5), [CdPt4(PPh3 )(8)(mu(3)-S)4][ClO4](2) (7), and [ZnPt4(PPh3)(8)(mu(3)-S)(4)][ClO4](2) (8), have been prepared from Pt-2(PPh3)(4)(mu-S)(2) (1) with appropriate zinc and cadmium substrates. The structures have been determined by single-crystal X-ray diffraction. The supporting anions play an active role in the structural assembly process. An unexpected disintegration complex [Pt-2(S2CH2)Cl(PPh3)(4)][PF6] (6) has also been isolated and characterized by single-crystal X-ray diffraction. The mechanism of the formation of 6 is proposed.