The isomorphous compounds NH4[(UO6)(2)(UO2)(9)(GeO4)(GeO3(OH))] (1), K[(UO6)(2)(UO2)(9)(GeO4)(GeO3(OH))] (2), Li3O[(UO6)(2)(UO2)(9)(GeO4)(GeO3(OH))] (3), and Ba[(UO6)(2)(UO2)(9)(GeO4)(2)] (4) were synthesized by hydrothermal reaction at 220 degrees C. The structures were determined using single crystal X-ray diffraction and refined to R-1 = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P (3) over bar 1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) angstrom(3), Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) angstrom(3), Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) angstrom(3), Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) angstrom(3), Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO2)(2+) uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation cation interaction, and accepts a different cation-cation interaction. The linkages between the U-centered polyhedra result in a relatively dense three-dimensional framework Ge and low-valence sites are located within cavities in the framework of U-polyhedra. Chemical, thermal, and spectroscopic characterizations are provided.