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Imine‐linked covalent organic frameworks (COFs) have been extensively studied in photocatalysis because of their easy synthesis and excellent crystallinity. The effect of imine‐bond orientation on the photocatalytic properties of COFs, however, is still rarely studied. Herein, we report two novel COFs with different orientations of imine bonds using oligo(phenylenevinylene) moieties. The COFs showed similar structures but great differences in their photoelectric properties. COF‐932 demonstrated a superior hydrogen evolution performance compared to COF‐923 when triethanolamine was used as the sacrificial agent. Interestingly, the use of ascorbic acid led to the protonation of the COFs, further altering the direction of electron transfer. The photocatalytic performances were increased to 23.4 and 0.73 mmol g−1 h−1 for protonated COF‐923 and COF‐932, respectively. This study provides a clear strategy for the design of imine‐linked COF‐based photocatalysts and advances the development of COFs. [ABSTRACT FROM AUTHOR]