We aimed to fabricate an olefin-linked COF by using commercially available tetramethylpyrazine, which can undergo a facile condensation reaction with terephthalaldehyde in the presence of benzoic anhydride and benzoic acid as modulator agents through the melt polymerization method (Figure ). To confirm the feasibility of this method, the model molecule 2,3,5,6-tetra((E)-styryl)pyrazine was successfully synthesized by the condensation reaction of tetramethylpyrazine and benzaldehyde catalyzed by benzoic anhydride (Figure , S1, S2 and Table ). Subsequently, we screened the melt polymerization and solvothermal synthetic conditions, including the amount of benzoic acid and benzoic anhydride, reaction solvent, reaction temperature and time, to fabricate a highly crystalline COF (Figure -S10 and Table ). As we envisioned, TMPZ, TPA, benzoic acid and benzoic anhydride in a molar ratio of 1:2:4:4 were sealed in a glass tube and heated at 180℃ for 5 days, leading to the generation of NKCOF-62 (Figure ). The formed COF monolith was washed with methanol and then dried at 80°C to obtain the purified NKCOF-62 with a yield of ~75%.