Li(VO2)3(TeO3)2

The title compound, lithium trisdioxidovanadium(V)] bistrioxidotellurium(IV)], contains chains of edge‐sharing distorted VO₆ octahedra. The pyramidal TeO₃ groups crosslink the chains into sheets. Finally, an Li⁺ cation adopting an unusual capped trigonal–bipyramidal LiO₆ geometry bridges the layers to complete a three‐dimensional structure.