In order to explore the influence of electron donor-acceptor structure on the photocatalytic performance of covalent organic frameworks (COFs), N,N"- p-acetonitrile-phenyl -1,4,5,8- naphthalimide (NBA) as basic building monomer was condensed with electron-donating tri (4- formyl) aniline (N-CHO) and electron-withdrawing 1,3,5- tri -(4- formyl) triazine (TFPT) to synthesize C=C linked NN-COF and NT-COF respectively. The average oxygen evolution rates of NN-COF and NT-COF were 303.73 μmol g-1 h-1 and 449.53 μmol g-1 h-1 with 7.4 mg Co(NO3)2?6H2O as cocatalyst. Through structure, morphology and photoelectric performance characterization, it was confirmed that compared with NN-COF, NT-COF showed tighter interlayer π-π stacking, wider visible light absorption range and better photo-generated carrier generation due to the electron-withdrawing ability and high planarity of its triazine unit. The electron-deficient naphthalimide unit of NT-COF is more conducive to the accumulation of photo-generated holes on its heteroatoms, thus catalyzing the oxidation reaction of water molecules more efficiently.