“…In the past 2 decades, crystalline materials, such as metal–organic frameworks (MOFs), covalent organic frameworks (COFs), or hydrogen-bonded organic frameworks (HOFs), have attracted extensive attention because of their unlimited structural diversity and functional tunability. − Due to the ability to custom-design the ligands with carrier molecules, tailor pore environments, and understand proton-transport pathways at the molecular level, crystalline materials provide a new platform for proton-conducting materials. − However, most of these crystalline materials focus on the conduction of crystals, the research studies on PEMs and PEMFCs are rare. ,− Owing to the unique characteristics such as rich hydrogen-bonding network and solution machinability, crystalline HOFs render a promising platform for proton conductivity and PEM materials. − The ligands used to construct single-component HOFs such as −COOH and −NH 2 can use their own functional groups to form hydrogen bonds, − but these traditional HOFs connected by weak hydrogen bonds have poor stability and, in most cases, the structures collapse under medium and high temperature conditions. Different from single-component HOFs, ionic two-component HOFs (also known as charge-assisted hydrogen bond frameworks) showed good stability due to the various hydrogen bond types and electrostatic interactions.…”