The air-stable phosphide, Ag6Ge10P12, was synthesized from its elements in gram amounts. As its structure is closely related to high-performance thermoelectric tetrahedrites (Ag6□Ge4Ge6P12≡ Cu6SSb4Cu6S12), we studied temperature dependent single-crystal X-ray diffraction experiments, quantum chemical calculations, and thermoelectric transport properties of spark plasma sintered and pristine, single crystalline samples, in order to give a comprehensive picture of its thermoelectric performance and its origin. The semiconducting character of this material is reflected in band structure calculations. Measurements of the thermal diffusivity exhibit a very low thermal conductivity, κ < 1 W m–1K–1, which is close to a phonon glass-like behavior, and has its origin in a strong local bonding asymmetry, induced by strong bonding of the phosphorus–germanium (Ge4+) covalent framework and weak bonding of lone-pair electrons (Ge2+). This chemical bond hierarchy creates a pronounced anisotropic behavior of the silver atoms leading to low-frequency vibrations and thermal damping. Combining this with a moderate electrical resistivity (ρ ∼ 15 mΩ cm) and a high Seebeck coefficient (S∼ 380 μV K–1) results in a remarkably high figure of merit (zT) of about 0.6 at 700 K. These results demonstrate that Ag6Ge10P12is one of the best thermoelectric phosphides and a promising new platform for the future development of thermoelectrics.