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 À 1 h À 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.Covalent organic frameworks (COFs), first realized in 2005, [1] are a new class of porous crystal framework materials composed of light elements (C, H, O, N) with twodimensional (2D) or three-dimensional (3D) network structures. [2] COFs have attracted great attention due to their high stability, low cost, large specific surface area, permanent porosity and open pore structure, and have shown great application prospects in various applications, such as gas adsorption/separation, [3] energy storage, [4] and catalysis. [5] In particular, the framework itself can be used as the best platform to study the structure-activity relationship because of its controllable structure, high crystallinity and regularity. [6] Several interesting studies have been published recently regarding the isomerism of covalent organic frameworks, since the study of property changes caused by