Two new mixed-valent tellurium oxides with vanadium(V), A4V6[Te24+Te6+]O24 (A = K and Rb), have been synthesized by hydrothermal and conventional solid state techniques. Their structures were determined by single-crystal X-ray diffraction analysis. These two iso-structural compounds exhibit layered structural topologies consisting of [V6Te3O24]4− anionic units. In these anionic structural units, a Te6+O6 octahedron is connected to six VO4 tetrahedra by corner-sharing to generate a [V6TeO24] unit, and each of these [V6TeO24] units are interconnected by sharing two Te4+O3 polyhedra to complete the infinite [V6Te3O24]4− sheets. Infrared spectroscopy, UV-Visible diffuse reflectance spectroscopy, and thermogravimetric analysis were also performed on these two compounds. Crystal data: K4V6Te3O24, trigonal, space group Rc (No. 167) with a = b = 9.7075(6) Å, c = 42.701(3) Å, V = 3484.9(4) Å3, and Z = 6; Rb4V6Te3O24, trigonal, space group Rc (No. 167) with a = b = 9.8399(9) Å, c = 43.012(4) Å, V = 3606.6(6) Å3, and Z = 6.