Thermoelectric (TE) research is not only a course of materials by discovery but also a seedbed of novel concepts and methodologies. Herein, the focus is on recent advances in three emerging paradigms: entropy engineering, phase‐boundary mapping, and liquid‐like TE materials in the context of thermodynamic routes. Specifically, entropy engineering is underpinned by the core effects of high‐entropy alloys; the extended solubility limit, the tendency to form a high‐symmetry crystal structure, severe lattice distortions, and sluggish diffusion processes afford large phase space for performance optimization, high electronic‐band degeneracy, rich multiscale microstructures, and low lattice thermal conductivity toward higher‐performance TE materials. Entropy engineering is successfully implemented in half‐Huesler and IV–VI compounds. In Zintl phases and skutterudites, the efficacy of phase‐boundary mapping is demonstrated through unraveling the profound relations among chemical compositions, mutual solubilities of constituent elements, phase instability, microstructures, and resulting TE properties at the operation temperatures. Attention is also given to liquid‐like TE materials that exhibit lattice thermal conductivity at lower than the amorphous limit due to intensive mobile ion disorder and reduced vibrational entropy. To conclude, an outlook on the development of next‐generation TE materials in line with these thermodynamic routes is given.

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We revisit the well-established Bi2Te3 via phase diagram engineering. Along with a phase diagram in hand, it is realized that the solubility of Ga in Bi2Te3 is coincident with the p–n transition zone in Ga–Bi2Te3 alloys. The best-performing n-type (Bi2Te3)0.93(Ga2Te5)0.07 possesses a peak zT ∼ 1.5 at 300 K, which is attributed to the reduced κ ∼ 1.8 W m–1 K–1 and the low-lying ρ. The p-type Bi1.99Ga0.01Te3 also exhibits a peak zT of 1.2 at 300 K. In other words, the addition of Ga leads to high-zT p-type or n-type bismuth-tellurides, which simplifies the conventional synthesis route that usually involves different dopants.