Directed ion transport is captured by tensor-resolved NMR.

Controlling the dimensionality of ion transport is a powerful strategy for designing high-performance electrolytes, yet direct experimental access to anisotropic ion dynamics at the molecular level remains limited. Here, we apply an orientation-selective NMR methodology to determine temperature-dependent diffusion and electrophoretic mobility tensors of the ionic liquid crystal C 12 mimBF 4 across its isotropic and smectic phases. The results reveal a pronounced reorganization of transport at the isotropic–smectic transition: isotropic, spatially homogeneous motion transforms into anisotropic transport with enhanced in-layer mobility and suppressed cross-layer migration. Despite this redistribution, orientationally averaged transport coefficients remain continuous across the transition, indicating that structural ordering redirects rather than amplifies ion motion. Electrophoretic mobilities show near-quantitative agreement with macroscopic conductivity, while only minor deviations from the Einstein–Smoluchowski relation are observed for the anions, consistent with weak ion–ion correlations. Our findings identify anions as the dominant charge carriers within polar channels and demonstrate how self-assembled structure enforces quasi-two-dimensional ion conduction. The approach provides a general framework for resolving anisotropic transport in soft matter electrolytes.