Charge transfer and mobility are essential for electrochemical processes in batteries, which need to be understood in detail for optimization, especially in the case of all-solid-state batteries. Wide line NMR is well-known in solid-state NMR and allows the quantification of ion mobility in ordered crystalline and amorphous structures. Temperature-dependent <sup>23</sup>Na-NMR is sensitive to ion mobility via longitudinal relaxation, but also via line analysis and transverse relaxation. As <sup>23</sup>Na is a spin 3/2 nucleus, <sup>23</sup>Na-NMR is also susceptible to electric field gradients caused by their nearest neighbor environment and, therefore, reflects not only the mobility of <sup>23</sup>Na<sup>+</sup> but also the molecular dynamics in the neighborhood, which are investigated in this paper. The named NMR methods were explored to study <sup>23</sup>Na<sup>+</sup> mobility in the solid electrolytes NaSICON (sodium (Na) Super Ionic CONductor, here Na<sub>3.4</sub>Zr<sub>2</sub>Si<sub>2.4</sub>P<sub>0.6</sub>O<sub>12</sub>), the salt NaTFSI (sodium bis(trifluoromethyl sulfonyl)imide), as well as in the polymer-based electrolytes PEO-NaSICON, PEO-NaTFSI, and PEO-NaTFSI-NaSICON.