Thermotropic Ionic Liquid Crystals (TILCs) have recently emerged as a smart class of organic electrolytes encoding the unique hierarchical self-assembling properties and stimuli-responsive mosaicity of mesophases featured by thermotropic liquid crystals with the efficient ion transport of ionic liquids. As a result, TILCs stand out as a promising electrolytic platform for energy storage (batteries/supercapacitors) and conversion (fuel cells/DSSCs) as they use industry-compatible and simple-to-implement manufacturing processes. The multi-scale correlation relating their structures and (an/cat)ionic transport properties is crucial to pave understanding of their ionic transport. A fundamental question of interest is here the influence of the dynamical mosaicity related to the average size of their self-assembled domains, with or without (w vs. w/o) dynamic grain boundaries. Remarkably, stimuli such as electric or magnetic field can be leveraged to sample (dis)order till ultimately reaching monodomains (eradication of mosaicity) to reveal inherent (i.e. defect-free) features of their ionic transport. Exploring this research endeavour, in this communication, the case study of an anionic conductive TILC (A-TILC) composed of an imidazolium-based cation with symmetrical n-alkyl chains (C18C18Im+) and a N(CN)2- anion featuring a Smectic A (SmA) mesophase (lamellar organization) will be deciphered by combining state-of-the-art (SoA) theoretical and experimental approaches. First, coarse-grained simulations derived from Martinelli will be presented to unravel its set of structural and dynamic descriptive parameters. Second, an unique operando experiment combining (synchrotron-based) SoA structural studies (SAXS+WAXS) with ionic transport measurements (probed by EIS) w vs. w/o a tuneable (0 up to 1T) magnetic field (Fig. 1) will be introduced, allowing in-depth study of the interplay linking its structure with its ion transport properties. In closing and beyond the case study of an A-TILC encoding a nanoconfined 2D transport within a SmA mesophase, we will illustrate the potential offered by TILCs to impart next generation (conversion/storage) energy devices with self-healing functionalities.