Novel sodium glycostannate precursors have been synthesized from sodium stannate and glycol reactants. These anionic precursors were investigated as potential starting materials towards the assembly of mesostructured tin oxide. The glycostannate precursors could be charge balanced with cationic surfactants, such as cetyltrimethylammonium bromide, in non-aqueous solutions to give composite structures in which the glycostannate anions remained structurally intact. Subsequent hydrolysis and condensation of these structures with acidic aqueous solutions gave mesostructured tin oxide materials. The initial formation and hydrolysis/condensation of these surfactant–glycostannate composites was followed by solid-state ¹¹⁹Sn NMR, thermal gravimetric analysis, powder X-ray diffraction, and transmission electron microscopy. Calcination of the final materials at 400 °C led to collapse of the mesostructure. Future attempts to stabilize such mesostructures to calcination utilizing silane, sulfate, or phosphate protecting groups should allow the formation of electroactive mesoporous tin oxide materials.