The nanostructural organization of liquid crystals (LC) creates unique opportunities for designing electrolytes with adaptive ion-transport properties. LC additives act as dynamic regulators of ion flow, balancing charge storage and energy release through local stimuli-responsive reorganization. LC functionalization has been shown to reduce self-discharge in supercapacitors, suppress dendrite formation in lithium–metal batteries, and enhance the ionic conductivity via self-assembled structures. However, the fundamental mechanisms behind these benefits remain poorly understood. Here, we investigate LiTFSI-based electrolytes doped with the mesogen 4-cyano-4′-pentylbiphenyl (5CB) using a range of solution- and solid-state NMR techniques. Heteronuclear Overhauser effect spectroscopy confirms molecular-level mixing across a broad LC concentration range. Pulsed-field gradient and electrophoretic NMR reveal composition-dependent trends in ion dynamics. Our findings show that ion mobility is governed not by LC alignment near electrode interfaces but rather by local LC concentration and specific ion–LC interactions. These results emphasize the importance of composition-driven and interfacial control of ion transport in LC-functionalized electrolytes over strategies that rely solely on mesogen alignment.