BaGa2Sb2 was obtained from a direct element combination reaction in a sealed graphite tube at 950 degreesC, and its structure was determined by single-crystal X-ray diffraction methods. It crystallizes in the orthorhombic space group Pnma (No. 62) with a = 25.454(5) Angstrom, b = 4.4421(9) Angstrom, c = 10.273(6) Angstrom, and Z = 8. The anionic [Ga2Sb6/3](2-) framework is assembled by the ethane-like dimeric [Sb3Ga-GaSb3] units sharing Sb atoms, forming parallel tunnels with a 26-membered ring cross section. These tunnels are filled with Ba atoms. The three-dimensional [Ga2Sb6/3](2-) framework features a new structure type. The compound satisfies the, classical Zintl concept: Band structure calculations indicate that the material is a semiconductor, and this is confirmed by spectroscopic experiments which show E-g similar to 0.35 eV. The calculations also suggest that the structure is stabilized by strong Ga-Ga covalent bonding interactions. Polycrystalline ingots of BaGa2Sb2 show room-temperature electrical conductivity of similar to 65 S/cm and a Seebeck coefficient of +65 muV/K.