Developing new materials for anhydrous proton conduction under high-temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as À C=NÀ , À OH, À N=NÀ and À CF 3 ) to improve the utilization efficiency and hostguest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H 3 PO 4 , COFs can realize a proton conductivity of 2.33 × 10 À 2 S cm À 1 under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80-160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high-temperature proton exchange membranes.

Developing new materials for anhydrous proton conduction under high-temperature conditions is significant and challenging. Herein, we create a series of highly crystalline covalent organic frameworks (COFs) via a pore engineering approach. We simultaneously engineer the pore geometry (generating concave dodecagonal nanopores) and pore surface (installing multiple functional groups such as À C=NÀ , À OH, À N=NÀ and À CF 3 ) to improve the utilization efficiency and hostguest interaction of proton carriers, hence benefiting the enhancement of anhydrous proton conduction. Upon loading with H 3 PO 4 , COFs can realize a proton conductivity of 2.33 × 10 À 2 S cm À 1 under anhydrous conditions, among the highest values of all COF materials. These materials demonstrate good stability and maintain high proton conductivity over a wide temperature range (80-160 °C). This work paves a new way for designing COFs for anhydrous proton conduction applications, which shows great potential as high-temperature proton exchange membranes.