This paper describes the complete assignment of the W-183 NMR spectra of the chiral polyoxometalates alpha(1)-[P2W17O61](10-) and alpha(1)-[YbP2W17O61](7-) in aqueous solution. These spectra display each 17 lines of equal intensity with a relatively narrow chemical shift distribution. The identification of signals is based on selective P-31-W-183 decoupling and recognition of particular sets of coupling constants for tungsten atoms around the lacunary site. Further assignment is obtained by W-183 2D-COSY NMR experiments. We demonstrate herewith a new way for the unambiguous assignment of W-183 NMR spectra of polyoxotungstates without any symmetry elements or tungsten atoms in special positions. This way relies on the correlation of the magnitude of (2)J(W-W) coupling constants with the geometry of oxo-bridges in polyoxotungstates. These results open the way to monitor interaction sites of chiral polyoxotungstates with organic ligands.