Jiahui Liu, Marek W. Urban
Abstract This perspective review delineates recent advances in poly(ionic liquids) (PILs) in the context of molecular events and nature‐inspired materials. PIL's structural uniqueness and versatility provide the opportunity to utilize a bottom‐up approach, which, when combined with top‐down nano‐ and micro‐manufacturing, may lead to numerous diversified applications. PILs’ features mark a turning point where biology and materials intersect, which will lead to new materials involving bio‐inspired self‐assembling building blocks, facilitating the platform for top‐down fabrication approaches. To achieve this, it is essential to disentangle the peculiar effects of chain topology from other factors, including but not limited to ion concentration, segmental dynamics, or side‐chain mobility, ultimately leading to a comprehensive model of the topology‐conductivity relationships. The ultimate goal is to relate the molecular events involved in polar and dipolar interactions to PILs' functional integrity, thereby enabling intended performance over time. The aim of this review is not to summarize recent advances in chemical and physical properties, but to identify how molecular events can influence the topology, morphology, and micro/nano‐manufacturing. Furthermore, the aim is to identify guiding principles and a framework for designing PILs by analyzing their structural features and the role of molecular events in various applications.