The strong excitonic effects widely exist in polymer-semiconductors and the large exciton binding energy (Eb) 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, theirEbcan be systematically regulated with minimumEbin TAPT-OMe. Guided by these results, the corresponding D-A COFs are synthesized, where TAPT-OMe-COF possesses the best activity in photocatalytic H2production and the activity trend of other COFs is associated with that of calculatedEbfor 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 smallerEbexhibits ~20 times higher activity than the parent COF.