Abstract Single crystals of CsGa 7 O 11 , RbGa 7 O 11 , and RbGa 4 In 5 O 14 were grown from alkali halide melts and their structures were characterized by single crystal and powder X‐ray diffraction. CsGa 7 O 11 and RbGa 7 O 11 adopt the same structure type, reminiscent of the hollandite structure type, as it contains nearly rectangular channels made up of two dimers of edge‐sharing GaO 6 octahedra, and two corner‐sharing octahedron/tetrahedron pairs. The structure of RbGa 4 In 5 O 14 is more complex and is comprised of indium octahedra, gallium trigonal bipyramids, and gallium tetrahedra, and contains similar sized tunnels as CsGa 7 O 11 and RbGa 7 O 11 . CsGa 7 O 11 and RbGa 4 In 5 O 14 were further characterized by TGA, ion exchange experiments, and DFT studies revealing that both structures are thermodynamically stable up to 850°C; however, CsGa 7 O 11 decomposes to GaO(OH) xH 2 O when heated in warm aqueous solutions. CsGa 7 O 11 undergoes ion exchange in both an aqueous solution of RbCl and a RbNO 3 melt, as predicted by DFT studies, where the ion exchange is more extensive in the RbNO 3 melt.