Ag-2[W6I14] and A(2-x)[W6I14] compounds with A = Na, Li were prepared from binary tungsten iodides (W3I12) and corresponding metal iodides. Their crystal structures are analyzed on the basis of X-ray diffraction data. Li-7 and Na-23 solid-state NMR measurements reveal that Li+ and Na+ ions are distributed over two sites in the respective structures. These results shed some new light on A(x)[M6I14] with A = alkali and M = Mo, W compounds being reported with x = 1 and 2, which exhibit photophysical properties. The lithium compound is an exception in the series of A(2-x)[W6I14] compounds, because it is the only compound which is soluble in water.