Pure polycrystalline phases and single crystals of four new quaternary alkali metal yttrium tellurites, NaYTe4O10, KY(TeO3)(2), RbY(TeO3)(2), and CsYTe3O8, have been prepared by solid-state and hydrothermal reactions using A(2)CO(3) (A = Na, K, Rb, and Cs), Y(NO3)(3)center dot 6H(2)O, Y2O3, and TeO2 as starting reagents. X-ray diffraction analyses suggest that NaYTe4O10 exhibits a highly symmetric three-dimensional (3D) framework consisting of YO8 square antiprisms and chains of TeO4 polyhedra. Within the framework, six- (6-) and eight-membered ring (8-MR) channels are observed. KY(TeO3)(2) and RbY(TeO3)(2) are isostructural to each other and reveal another 3D framework with structures containing YO6 octahedra and TeO3 trigonal pyramids with 4-MR and 12-MR channels. CsYTe3O8 shows a hexagonal tungsten bronze (HTB)-like topology composed of hexagonal tungsten oxide-like layers of TeO4 polyhedra and YO6 octahedral linkers with 3-MR and 6-MR channels. Thermal analyses, elemental analyses, and spectroscopic characterizations, such as UV-vis diffuse reflectance and infrared spectra, are presented, as are local dipole moment calculations for the constituent asymmetric polyhedra TeO3 and TeO4.