Two new Sn2+-W6+-oxides, Sn2WO5 and Sn3WO6, have been synthesized hydrothermally, and their structures have been determined by single-crystal X-ray diffraction methods. Both materials exhibit layered structural topologies consisting of two edge-shared WO6 octahedra connected to SnO3 and SnO4 polyhedra. Both the W6+ and Sn2+ cations are in locally asymmetric coordination environments attributable to second-order Jahn-Teller effects. Infrared and Raman spectroscopy, UV-vis diffuse reflectance spectroscopy, and thermogravimetric analysis were also performed on the reported materials. Theoretical calculations using the tight binding linear muffin tin orbital method agree with the observed electronic properties of these materials and indicate that the stereoactive lone pair on the Sn2+ is similar for both materials. Crystal data: Sn2WO5, monoclinic, space group P2(1)/n (No. 14), a = 7.994(2) angstrom, b = 13.712(4) angstrom, c = 10.383(3) angstrom, beta = 110.507(3)degrees, V = 1066.0(5) angstrom(3), and Z = 4; Sn3MO6, monoclinic, C2/c (No. 15), a = 12.758(3) angstrom, b = 8.0838(16) angstrom, c = 13.865(3) angstrom, beta = 112.49(3) degrees, V = 1321.2(5) angstrom(3), and Z= 8.