Polyoxometalates such as ammonium paratungstate (APT) constitute an important class of metal oxides with applications for catalysis, (opto)electronics, and functional materials. Structural analyses of solid polyoxometalates mostly rely on X-ray or neutron diffraction techniques, which are largely limited to compounds that can be isolated with long-range crystallographic order. While 183 W NMR has been shown to probe polyoxotungstate structures and dynamics in solution, its application to solids has been extremely limited. Here, state-of-the-art methods for the detection of solid-state 183 W NMR spectra are tested and compared for APT in different hydration states. The highly resolved solid-state spectra distinguish each crystallographically distinct site in the tungstate structure. Furthermore, the 183 W chemical shifts are shown to be highly sensitive to the local structure, dynamics, and symmetry of APT, establishing solid-state 183 W NMR spectroscopy as a potent probe for analysis of polyoxotungstates and other tungsten-derived materials to complement solution NMR and diffraction-based techniques.