A series of chiral M6M′8 cluster compounds having twelve free carboxylate groups, [M6M′8(D-pen-N,S)12X]5− (M/M′/X = PdII/AgI/Cl− ([1]5−), PdII/AgI/Br− ([2]5−), PdII/AgI/I− ([3]5−), NiII/AgI/Cl− ([4]5−), PtII/AgI/Cl− ([5]5−), PdII/CuI/Cl− ([6]5−); D-H2pen = D-penicillamine), in which six cis-[M(D-pen-N,S)2]2− square-planar units are bound to a [M′8X]7+ cubic core through sulfur-bridges, was synthesized by the reactions of cis-[M(D-pen-N,S)2]2− with M′ in water in the presence of halide ions. These M6M′8 clusters readily reacted with La3+ in aqueous buffer to form LaIII2M6M′8 heterotrimetallic compounds, La2[1](CH3COO), La2[2](CH3COO), La2[3](CH3COO), La2[4](CH3COO), La2[5](CH3COO) and La2[6]Cl, in which the M6M′8 cluster units are linked by La3+ ions through carboxylate groups in a 1 : 2 ratio. While the LaIII2M6AgI8 compounds derived from [1]5−, [2]5−, [3]5−, [4]5− and [5]5− have a 1D helix supramolecular structure with a right-handedness, the LaIII2PdII6CuI8 compound derived from [6]5− has a 2D sheet-like structure with a triangular grid of the PdII6CuI8 cluster units. When aqueous HCl was added to the reaction solution of [6]5− and La3+, another LaIII2PdII6CuI8 heterotrimetallic compound, La2[6]Cl·HCl, in which the PdII6CuI8 cluster units are linked by La3+ ions to form a 2D structure with a rectangular grid, was produced. The solid-state structures of these LaIII2M6M′8 compounds, determined by single-crystal X-ray crystallography, along with the spectroscopic properties of the M6M′8 cluster compounds in solution, are described.