We report the synthesis and characterization of a new quaternary heteroanionic chalcogenide phase, Ba3GeTeS4. A single-crystal X-ray diffraction study of a yellow-colored crystal of Ba3GeTeS4 shows that the compound is stoichiometric and crystallizes in the orthorhombic Cmcm space group having cell parameters of a ​= ​6.8583(12) Å, b ​= ​16.207(3) Å, c ​= ​9.6239(19) Å, with four formula units (Z ​= ​4) per unit cell. The unit cell of the structure consists of two Ba, one Ge, one Te, and two S sites. All the crystallographically independent atoms occupy special positions. The Ba3GeTeS4 structure is made up of zero-dimensional [GeS4]4– anionic units along with Ba2+ cations, each of that is surrounded by the Te and S atoms. An optical UV–Vis absorption study on a polycrystalline sample of Ba3GeTeS4 establishes its semiconducting nature with a direct bandgap of 2.5(2) eV consistent with the yellow color of the sample. The polycrystalline Ba3GeTeS4 shows an extremely low value of thermal conductivity (∼0.46 W/mK) at 723 ​K. The ab-initio DFT calculations predict a high value of the thermoelectric figure of merit (zT ​> ​1) for the hole doped-Ba3GeTeS4 sample. The crystal orbital Hamilton population (COHP) analysis shows that the Ge–S bonds are strongest in the structure, while the strengths of the Ba–S and Ba–Te interactions are similar. © 2023 Elsevier Inc.