PbTeF 6 crystallizes with monoclinic symmetry (space group P2 1 /c) and the unit cell parametersa = 462.5(1) pm, b = 1281.2(2) pm,c = 851.9(1) pm, β = 102.36(1) o , Z = 4.Its crystal structure has been solved by a Rietveld analysis of its X-ray powder pattern and refined to the final agreement factorsR b = 0.059 and R p = 0.073. The Pb I I and Te I V atoms are respectively seven- and five-fold coordinated and their lone pair E is stereochemically active.By sharing edges, the PbF 7 E polyhedra constitute infinite zig-zag chains parallel to 0x. These chains are connected to each other by sharing their free corners with the TeF 5 E polyhedra, one of the corners being non-bridging.Structural relationships with ReO 3 -type materials are described and analyzed.