Microporous materials have the potential to enable new low energy separation processes due to their superb textural properties and structural diversity, yet these materials are facing practical challenges in large-scale applications. Opportunities for advancing microporous sorbents lie in a technology that can bridge the gap between high-performance materials and scalable separation devices. This perspective article discusses the current state of the art and the potential of the fiber sorbent-based separation processes by highlighting the structure-property-performance relationships, candidate porous materials, and application areas.