The hydrothermal reaction of Th(NO3)(4)(.)xH(2)O with V2O5 and H6TeO6 at 200 degrees C under autogenously generated pressure results in the formation of Th(VO2)(2)(TeO6)(H2O)(2) as a pure phase. The single-crystal X-ray data indicate that Th(VO2)(2)(TeO6)(H2O)(2) possesses a three-dimensional structure constructed from ThO9 tricapped trigonal prisms, VO5 distorted square pyramids, VO4 distorted tetrahedra, and TeO6 distorted octahedra. Both of the vanadium polyhedra contain VO2+ vanadyl units with two short V = O bond distances. The tellurate octahedron is tetragonally distorted and utilizes all of its oxygen atoms to bond to adjacent metal centers, sharing edges with ThO9 and VO5 units, and corners with two ThO9, one VO5, and two VO4 polyhedra. Crystallographic data: Th(VO2)(2)(TeO6)(H2O)(2), orthorhombic, space group Pbca, a = 12.6921(7), b = 11.5593(7), c = 13.0950(8) angstrom, Z = 8 (T = 193 K). The UV-vis diffuse reflectance spectrum of Th(VO2)(2)(TeO6)(H2O)(2) shows vanadyl-based charge-transfer absorption features. Th(VO2)(2)(TeO6)(H2O)(2) decomposes primarily to Th(VO3)(4) when heated at 600 degrees C in air.