Large Seebeck coefficients induced by high degeneracy of conduction band minimum, and low intrinsic lattice thermal conductivity originated from large lattice vibrational anharmonicity render Mg3Sb2 as a promising n-type thermoelectric material. Herein, we demonstrated unique concentration-dependent occupation behaviors of Cu in Mg3.4Sb1.5Bi0.49Te0.01 matrix, evidenced by structural characterization and transport property measurements. It is found that Cu atoms prefer to enter the interstitial lattice sites in Mg3Sb2 host with low doping level (Mg3.4Sb1.5Bi0.49Te0.01 + x% Cu, x
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