AbstractThe reaction of elemental barium, gallium and either bismuth or antimony with small amounts of barium peroxide yields yellow platelet‐shaped crystals of Ba9[GaO4]3Sb (1) and orange platelet‐shaped crystals of Ba9[GaO4]3Bi (2), respectively. Using arsenic instead of bismuth or antimony, black metallic shining crystals of Ba2[GaO2As] (3) are obtained. The crystals of these compounds are air‐sensitive and have been characterized by single crystal X‐ray diffraction and energy dispersive X‐ray fluorescence spectroscopy. 1 and 2 contain tetrahedral [GaO4]5− units and isolated Sb3− and Bi3− ions coordinated solely by Ba2+‐ions in icosahedral and cuboctahedral fashion. 3 is built of [GaO2As2/2]4− tetrahedra, which are linked via the As atoms to infinite chains. This polyanion can be perceived as a typical Zintl anion, which is partially oxidized.