The Dawson-type arsenato-phosphato-tungstate alpha-[AsPW18O62](6-) has been prepared and unambiguously identified for the first time. A comparative study. including the four other already known compounds, the symmetric alpha-[X2W18O62](6-) and unsymmetric alpha-[H4XW18O62](7-) for X = P-V, As-V, has been performed by spectroscopic W-183 and P-31 NMR. 2-D W-183 INADEQUATE experiments were systematically employed to unequivocally verify structures, assign all resonances, and determine precisely (2)J(W-O-W) scalar couplings. The effects of P/As substitutions, generating unsymmetric structures, on the NMR observables delta(W-183), delta(P-31), (2)J(W-O-W), and (2)J(W-O-P) are discussed in relation to their bond length and bond angle alteration. General trends with respect to NMR parameter variations have been found when filling central cavities with P or As atoms, with less pronounced effects for As than for P. In addition, NMR characterization of three other isomers, i.e., beta-[X2W18O62](6-) and [As2W18O62](6-), were also provided for comparison. The present NMR results could serve as representative reference data for understanding the relationship between structure and NMR observables in polyoxotungstates.