Abstract The dependence of ionic transport on crystal orientations in NaSICON-type solid electrolytes is studied on flux-grown M₃Sc₂(PO₄)₃ (M = Na, Ag) single crystals with well-defined facets. Herein, we provide the first impedance spectroscopy study to characterize ion conduction along different crystallographic orientations in this important class of materials for electrochemical energy storage systems. Moreover, we used single crystal x-ray diffraction, differential scanning calorimetry, ²³Na NMR spin-lattice relaxation measurements, and ab initio molecular dynamics simulations to study the interplay of structure and ion transport taking place at different length scales. We conclude that the phase behavior in NaSICON-type materials is strongly linked to ion diffusion. At room temperature, ionic conductivity is slightly anisotropic along the crystallographic orientations [001] and [100]. The slightly different activation energies are related to diffusion bottlenecks solely changing along [001]. This change is caused by anisotropic thermal lattice expansion. With increasing temperature, ion transport increasingly becomes isotropic finally resulting in an order-disorder phase transition from C2/c to R−3c. This phase transition is associated with a clear change in activation energy solely along [001]; it can be traced back to the increasing jump distance along this crystal orientation with temperature. Astonishingly, changing the ionic charge carrier, i.e. when going from Na⁺ to Ag⁺, shifts the phase transition temperature by 140 K towards lower temperature. The Arrhenius behavior remains, however, similar. This finding is related to the higher mobility of Ag⁺ in the NaSICON framework leading to isotropic ion diffusion at much lower temperatures. Overall, flux-grown M₃Sc₂(PO₄)₃ allowed us to show that ionic transport parameters and phase stability sensitively depend on crystal chemistry.