Solid solutions Co 3-x Zn x TeO 6 (x = 0-3) were prepared both in polycrystalline and single-crystalline form using solid state reactions and chemical vapour transport reactions, respectively. Miscibility between the isotypic end members was established over the complete range (C2/c, Z = 12, a ≈ 14.85, b ≈ 8.83, c ≈ 10.34 Å, ≈ 93°). Crystal structure determinations, performed on basis of single crystal laboratory X-ray (at 295 K) and synchrotron (at 10 and 100 K) data of Co 3 TeO 6 and selected solid solutions, revealed no structural phase transition and allowed a detailed insight into the Co → Zn substitution mechanism. The coordination polyhedra of the five crystallographically independent M 2+ cations are distorted octahedra (for three cations), one distorted tetrahedron and one distorted square [a] Details of all crystal structure investigations can be obtained from Fachinformationszentrum Karlsruhe,