The n-type I-V-VI2 AgBiSe2 features intrinsically low K due to the anharmonicity of chemical bonds. Experimentally-determined isothermal section guides the starting compositions for the following AgBiSe2-based alloys. Among the undoped alloys, the Ag25Bi25Se50 exhibits a highest peak of zT similar to 0.75, and yet the neighboring Ag20Bi27.5Se52.5, which involves a Se-rich liquid phase, has a much lower zT similar to 0.3 at 748 K, respectively. With the incorporation of Ge, the (GeSe)(0.03)(AgBiSe2)0.97 exhibits an ultralow K similar to 0.3 (W/mK), owing to the formation of Bi2Se3 nano-precipitate in the size of 20-40 nm. Additionally, the moire fringes with a periodicity of 0.25 nm are observed in the Bi2Se3 nano-precipitate, implying the presence of local mass fluctuation and superlattice, which could further lead to enhancing phonon scattering and reduced K. As a result, the ultra-low K similar to 0.3 (W/mK) boosts the peak of zT up to zT similar to 1.05 in n-type (GeSe)(0.03)(AgBiSe2)(0.97), which shows a 140% enhancement compared with that of the undoped AgBiSe2. (c) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.