The present invention uses a step-by-step synthesis strategy to prepare a series of aromatic azo compound building blocks (named after Azo-R, R=NHBoc, NH 2 , p‑phenyl‑NHBoc, CHO, B(OH) 2 , CN, CH 2 CN, etc.), and then used them as precursors to synthesize a series of stable, highly crystalline and high specific surface novel covalent organic frameworks (COFs) materials. Through characterization, it is found that these COFs have high specific surface area and excellent chemical stability, and can be used in various common organic solvents (acetone, dichloromethane, DMF, etc.), concentrated hydrochloric acid (12M), concentrated alkali NaOH (12M), Stable in boiling water. In addition, they show good hydrophilicity and high water vapor adsorption capacity, which make this type of COFs an ideal proton-conducting material. After loading phosphoric acid, these COFs achieved ultra-high proton conductivity with a conductivity of 1.13×10 ‑ 1 S / cm, this value can be compared with the value of commercial Nafion (~1.1×10 ‑1 S / cm) comparable. These COFs can be easily fabricated into proton exchange membrane devices and applied to hydrogen-oxygen fuel cells.