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Ga3B crystallizes in the hexagonal P6_3/mmc space group. The structure is one-dimensional and consists of two Ga3B ribbons oriented in the (0, 0, 1) direction. Ga is bonded in a distorted L-shaped geometry to two equivalent B atoms. Both Ga–B bond lengths are 2.31 Å. B is bonded to six equivalent Ga atoms to form distorted face-sharing BGa6 pentagonal pyramids.
Ga3B is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Ga is bonded to eight equivalent Ga and four equivalent B atoms to form GaGa8B4 cuboctahedra that share corners with twelve equivalent GaGa8B4 cuboctahedra, edges with eight equivalent BGa12 cuboctahedra, edges with sixteen equivalent GaGa8B4 cuboctahedra, faces with four equivalent BGa12 cuboctahedra, and faces with fourteen equivalent GaGa8B4 cuboctahedra. All Ga–Ga bond lengths are 2.80 Å. All Ga–B bond lengths are 2.80 Å. B is bonded to twelve equivalent Ga atoms to form BGa12 cuboctahedra that share corners with twelve equivalent BGa12 cuboctahedra, edges with twenty-four equivalent GaGa8B4 cuboctahedra, faces with six equivalent BGa12 cuboctahedra, and faces with twelve equivalent GaGa8B4 cuboctahedra.