A monophasic polycrystalline sample of Ba2Ge2Te5 has been synthesized for the first time using the sealed tube solid-state method. The Rietveld refinement of a polycrystalline Ba2Ge2Te5 and a single crystal X-ray diffraction study confirm that Ba2Ge2Te5 crystallizes in the orthorhombic polar C2v9-Pna21 space group. Each of the Ge atoms in the Ba2Ge2Te5 structure is covalently connected to one Ge and three Te atoms making one-dimensional (1D) chains of 1∞[Ge2Te5]4− that are separated by Ba2+ cations. The (Ba2+)2(Ge3+)2(Te2−)5 can be charge-balanced as per the Zintl-Klemm concept. A resistivity study of Ba2Ge2Te5 shows a metallic behavior till 18 K below which metal to insulator transition was observed. Thermal conductivity of Ba2Ge2Te5 was found to decrease gradually on heating the sample with a minimum of about 0.41 Wm–1K–1 at 773 K. The DFT studies predict semiconducting nature for Ba2Ge2Te5 with a narrow indirect bandgap of about 0.6 eV. © 2021 Elsevier Ltd