Dynamic Mosaicity Modulates Ion Transport in Stimuli‐Responsive Liquid Crystal Electrolytes

Abstract Structural mosaicity and defects are ubiquitous across materials and critically influence functional properties, from semiconductors to biological membranes. In soft matter electrolytes, these features remain difficult to probe and exploit due to complex synthesis and limited long‐range structural order. A dimensionally tunable model system based on thermotropic ionic liquid crystals (TILCs) is introduced to investigate the interplay between structural mosaicity and ion transport. In two‐dimensional (2D) anion‐conducting smectic TILCs, ion transport exhibits a pronounced anisotropy—up to four orders of magnitude at 70 °C—attributed to ion confinement within 0.7–1.2 nm‐thick lamellar sublayers. In situ and operando synchrotron X‐ray scattering combined with electrochemical analyses reveal direct experimental evidence of a strong correlation between long‐range supramolecular organization, quantified via dynamic mosaicity, and mesoscopic ion transport. Application of a 1 Tesla magnetic field enhances domain size by 1.5× and boosts conductivity threefold, demonstrating stimuli‐responsive, mosaicity‐controlled ionic transport. These findings establish a generalizable structure–function framework for confined ion conduction in soft materials and bridge concepts from thermotropic liquid crystals to lyotropic phases, biological assemblies, and organic semiconductors. Positioning dynamic mosaicity as a key design parameter, this work lays the foundation for rational development of adaptive, self‐organized electrolyte systems for energy storage and conversion, ionotronics, and bioinspired ionic devices.