Covalent organic frameworks (COFs) with a donor-acceptor (D-A) architecture have been investigated as prospective semiconducting materials, particularly for photocatalytic processes. The incorporation of electron donating and accepting moieties into the COF backbone creates nano heterojunctions, enhancing efficient light absorption, charge separation, and charge transport. Herein, three pyrene-based COFs were well designed for the aerobic coupling of amines under air atmosphere with blue-LED irradiation. Among the three COFs, the Py-Por-COF with D-A structure exhibits the highest photocatalytic performance and demonstrates a remarkable apparent quantum efficiency of 11.3 % at 420 nm. In addition, the Py-Por-COF maintains a good level of crystallinity and high yield even undergone four cycles, showcasing the exceptional potential of D-A structure COFs in the field of photocatalytic organic transformation.