Advancements in membrane-based separation hinge on the design of materials that transcend conventional limitations. Microporous materials, including metal–organic frameworks (MOFs), covalent–organic frameworks (COFs), macrocycles, and porous organic cages (POCs) offer unprecedented control over pore architecture, chemical functionality, and transport properties, making them promising candidates for next-generation membrane technologies. The well-defined and tunable micropores provide a pathway to directly address the permeability-selectivity trade-off inherent in conventional polymer membranes. Here, this review explores the latest advancements in these four representative microporous membranes, emphasizing their breakthroughs in hydrocarbon separation, liquid-phase molecular sieving, and ion-selective transport, particularly focusing on their structure-performance relationships. While their tailored structures enable exceptional performance, practical adoption requires overcoming hurdles in scalability, durability, and compatibility with industrial processes. By offering insights into membrane structure optimization and innovative design strategies, this review provides a roadmap for advancing microporous membranes from laboratory innovation to real-world implementation, ultimately supporting global sustainability goals through energy-efficient separation processes.