The strong excitonic effects widely exist in polymer-semiconductors and the large exciton binding energy (E ) seriously limits their photocatalysis. Herein, density functional theory (DFT) calculations are conducted to assess band alignment and charge transfer feature of potential donor-acceptor (D-A) covalent organic frameworks (COFs), using 1,3,5-tris(4-aminophenyl)triazine (TAPT) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) as acceptors and tereph-thaldehydes functionalized diverse groups as donors. Given the discernable D-A interaction strengths in the D-A pairs, their E can be systematically regulated with minimum E in TAPT-OMe. Guided by these results, the corresponding D-A COFs are synthesized, where TAPT-OMe-COF possesses the best activity in photocatalytic H production and the activity trend of other COFs is associated with that of calculated E for the D-A pairs. In addition, further alkyne cycloaddition for the imine linkage in the COFs greatly improves the stability and the resulting TAPT-OMe-alkyne-COF with a substantially smaller E exhibits ~20 times higher activity than the parent COF.