Covalent‐organic frameworks (COFs) have been recognized as a new type of promising photocatalysts for hydrogen evolution. To investigate how different functional groups attached in the backbone of COFs affect the overall photocatalytic H2 evolution, for the first time, we selected and synthesized a series of ketoenamine‐based COFs with the same host framework as model system. It includes TpPa−COF−X (X=−H, −(CH3)2, and −NO2) with three different groups attached in the backbone of TpPa−COF. We systematically investigated the differences in morphology, light‐absorption intensity and band gap of these 2D COFs. The results of photocatalytic H2 evolution measurements indicate that the TpPa−COF−(CH3)2 shows the best activity, while the activity of TpPa−COF−NO2 is relatively low compared to that of other two COFs in the system. Moreover, the separation ability of photogenerated charge was also followed the order of TpPa−COF−(CH3)2>TpPa−COF>TpPa−COF−NO2. The best photocatalytic H2 production performance of TpPa−COF−(CH3)2 in these systems should be mainly attributed to the better electron‐donating ability of −CH3 groups compared to −H or −NO2 group, which result in more efficient charge transferring in the inner of the material. This work demonstrates that reasonably adding electron‐donating group in TpPa−COFs can lead to a better photocatalytic H2 evolution activity, and which is meaningful for further design of efficient COF‐based photocatalysts for H2 evolution. Photocatalysis: A series ketoenamine‐based COFs of TpPa−COF−X (X=−H, −(CH3)2, and −NO2) exhibit significant difference on the visible light absorbance and efficiency of photocatalytic H2 evolution, which can be attributed to strengthen charge carrier mobilities both in‐plane and in the stacking direction because of the electron‐donating groups.