A new type-I clathrate, Ba₈Cu₁₄Ge₆P₂₆, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba₈Cu₁₄Ge₆P₂₆ crystallizes in the cubic space group Pmn (no. 223). Ba₈Cu₁₄Ge₆P₂₆ is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba₈Cu₁₄Ge₆P₂₆ were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba₈Cu₁₄Ge₆P₂₆ is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m⁻¹ K⁻¹ at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba₈Cu₁₄Ge₆P₂₆ approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm⁻¹ K⁻². The thermoelectric efficiency of Ba₈Cu₁₄Ge₆P₂₆ is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700–850 K temperature region, including all tetrel-free clathrates. Ba₈Cu₁₄Ge₆P₂₆ expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba₈Cu₁₄Ge₆P₂₆ a strong candidate as a novel and efficient thermoelectric material.