Lithium halides (LiX) are important additives in organometallic chemistry, serving as pivotal agents that can modulate the reactivity and selectivity of organic reagents. The turbo Grignard reagent stands out as an emblematic example wherein the addition of lithium chloride empowers the performance of the organomagnesium species, enabling accelerated reaction rates, enhanced selectivity, and improved sensitivity. In fact, the literature indicates that LiX play a vital role in a multitude of chemical processes, establishing high-yield stereoselective aldol reactions, enhancing the reducing strength of inorganic salts, controlling polymer properties, and improving permeation and separation rates of polymeric membranes. Moreover, LiX constitute promising candidates for transition metal-free cathodes in batteries. As research in this field continues to evolve, and the synergistic interplay between LiX and organic reagents promises to unlock new pathways in chemical synthesis, it becomes essential to gain a comprehensive understanding of the chemistry of LiX. The task is challenging since numerous attempts to characterize LiX in organic solutions have evidenced a remarkable structural diversity. Depending on the conditions imposed, a diversity of moieties with varying nature and degrees of association can be expected. Accordingly, monomeric forms, as dimers, pseudo-cubanes, ladder-like structures, bridged forms, tetramers in double-dimeric arrangement, polymers, and ionic species have been detected (Figure ). It is therefore evident that LiX do not conform to a traditional identification as single, well-defined structures. Rather, they comprise an ensemble of morphologies that depend on the experimental conditions.