A new clathrate solid solution Ba8Cu16 − xAuxP30 (x = 4, 8, 12) was synthesized by a high-temperature solid-state annealing method. The crystal structures of Ba8Cu16 − xAuxP30 were determined by single crystal x-ray diffraction. This clathrate solid solution crystallizes in the orthorhombic superstructure of clathrate-I type with 23 crystallographically independent framework sites, eight of them are occupied by Au/Cu and 15 are exclusively occupied by P atoms. The distribution of Au and Cu atoms over these eight framework sites is not random with a clear preference for Au to occupy the largest (Au/Cu)P4 tetrahedra in the framework. The thermal stability and thermoelectric properties of the Ba8Cu16 − xAuxP30 solid solution were evaluated. Low thermal conductivity was achieved for Ba8Cu16 − xAuxP30 due to the combination of the host–guest crystal structure with rattling Ba atoms with the presence of heavy Au atoms and substitutional Cu/Au disorder in the clathrate framework.
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