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The rapid transformation of the global energy structure has promoted the broad application of lithium-ion batteries. The efficient extraction of lithium, which is a core raw material for lithium-ion batteries, has become a crucial step in the new energy sector. Crystalline porous materials (CPMs) with distinct chemical properties and versatile topological structures are promising for the separation of Li<sup>+</sup> ions. Herein, we systematically review the structural features of CPMs, particularly metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), for lithium-ion adsorption and separation, encompassing the latest advancements in adsorption and membrane-based technologies. By analyzing the core mechanisms underlying lithium ions' selective recognition and transport, such as ion exchange, chelation coordination, and sieving effects, this study reveals the structure-performance relationship for Li<sup>+</sup> ion separation. It is further elucidated that CPMs typically employ synergistic mechanisms, integrating multiple recognition pathways to enhance performance. Research indicates that the structural flexibility of MOFs and the chemical stability of COFs enable them to exhibit both high selectivity and high capacity in Li<sup>+</sup> ion adsorption. Functional modification and synthesis of composite materials help the adsorption and membrane separation process based on CPMs further overcome the limitations of traditional separation technologies. Finally, this review summarizes the challenges CPMs face in practical applications, outlines their future development directions for sustainable lithium resource development, and provides theoretical and practical references for the next generation of efficient lithium separation materials.