Synthetic Cs(VO2)3(TeO3)2 is built up from infinite sheets of distorted octahedral VVO6 groups, sharing vertices. These octahedral layers are “capped” by Te atoms (as parts of pyramidal [TeIVO3]2– groups) on both faces of each V/O sheet, with inter‐layer, 12‐coordinate, Cs+ cations providing charge compensation. Cs(VO2)3(TeO3)2 is isostructural with M(VO2)3(SeO3)2 (M = NH4, K). Crystal data: Cs(VO2)3(TeO3)2, Mr = 732.93, hexagonal, space group P63 (No. 173), a = 7.2351(9) Å, c = 11.584(2) Å, V = 525.1(2) Å3, Z = 2, R(F) = 0.030, wR(F 2) = 0.063.