Five new compounds in the AxMTeO6 family were prepared and structurally characterized: Li2GeTeO6, Na2TiTeO6, Na2SnTeO6, and two forms of Na2GeTeO6. All compounds are layered structures based on various stacking arrangements of MTeO62- layers. Structural characterizations were carried out using a variety of tools, including Rietveld refinements of x-ray and neutron powder diffraction data, solid state MAS NMR and Raman spectroscopy. With the exception of Na2TiTeO6, the MTeO62-layers show a high degree of M4+/Te6+ order, but various degrees of disorder are present in the stacking of these layers. Disorder in the layer stacking favors the ilmenite structure, where both M4+ and Te6+ centered octahedra share faces with the AO6 octahedra. Coherent layer stacking favors an ordered variation of the α-TlSbO3 structure, where the AO6 octahedra preferentially share faces with either the MO6 or the TeO6 octahedra.