With the increasingly serious environmental pollution and intensified energy crisis, exploitation and utilization of new kinds of clean energy resources are imperative. Among them, thermoelectric (TE) conversion technology based on highperformance TE materials enables direct energy conversion between heat and electricity through the movement of internal phonons and charge carriers. [1][2][3][4] It has shown extensive and important prospects in power generation using industrial waste heat and electronic refrigeration. [5] The energy conversion efficiency of a TE material is mainly determined by its dimensionless figure of merit, defined as zT = σS 2 T/(κ L + κ e ), where σ, S, T, κ L , and κ e are the electrical conductivity, Seebeck coefficient, absolute temperature, lattice thermal conductivity, and electronic thermal conductivity, respectively. The general criteria for high zTs require high crystal symmetry for materials, many valleys (carrier pockets) near the Fermi level, heavy elements with small electronegativity differences between the constituent elements, or complex crystal structure, etc. [6][7][8][9][10] For the constituent elements in the same group such as S, Se, and Te, the heavy one (Te and Se) always has large atomic mass for low κ L and more covalent bonding character for large carrier mobility (µ H ) and thus outstanding electrical transports. [10] Therefore, the zTs are usually high in tellurides and selenides, but they are low in sulfides. This is the general phenomenon that has been observed in those well-known TE materials such as Bi 2 X 3 -, SnX-, and PbX-based compounds (X = S, Se, and Te). As shown in Figure 1, the zT values gradually improve as the anion element change from S to Se and then to Te. However, the case is different in Cu 2 X-based liquidlike TE materials that are among the hottest materials in recent TE study. They possess exceptionally low thermal conductivity and excellent zTs with the values of 1.7-1.9 for Cu 2 S, 1.5-2.3 for Cu 2 Se, and 0.4-1.1 for Cu 2 Te (see Figure 1). [48][49][50][51][52][53][54][55][56][57][58][59][60][61][62] It is quite abnormal and interesting that the zT in Cu 2 Te is lower than those in Cu 2 S and Cu 2 Se. As we known, tellurium is less electronegative, thus the chemical bonds between Cu and Te should be less ionic as compared with those in Cu 2 S and Cu 2 Se, which is beneficial for large µ H and electrical transports. Besides, the κ L in Cu 2 Te is expected lower than or similar to those in Cu 2 S and Cu 2 Se because tellurium is much heavier than sulfur and Most of the state-of-the-art thermoelectric (TE) materials exhibit high crystal symmetry, multiple valleys near the Fermi level, heavy constituent elements with small electronegativity differences, or complex crystal structure. Typically, such general features have been well observed in those well-known TE materials such as Bi 2 X 3 -, SnX-, and PbX-based compounds (X = S, Se, and Te). The performance is usually high in the materials with heavy constituent elements such as Te and Se, bu...