As a class of the efficacious photocatalysts for water-splitting, conjugated polymers (CPs) have drawn considerable attention in recent years. However, the unexpectedly fast charge recombination always constricts their further application, leading to poor photocatalytic behavior. Here, we report a series of dibenzothiophene-S,S-dioxide-based polymers with electron-property-dependent reactivity as well as their photocatalysis in hydrogen evolution. The results reveal that the introduction of a secondary acceptor unit into the repeating units of a CP skeleton is an effective method to enhance the photocatalytic hydrogen production activity, which is conducive to the separation and transport of photogenerated charge carriers. Therefore, the Pt-free B-SO and C₃N₃-SO photocatalysts in an A₁–π–A₂ form exhibit a competitive hydrogen evolution rate (HER) of 778 and 1603 μmol g^–1 h^–1 under visible light, respectively. Notably, under the same conditions, the 3 wt % Pt-modified B-SO and C₃N₃-SO provide a satisfactory HER of 1253 and 2966 μmol g^–1 h^–1, respectively. Our study proffered an effective strategy for enhancing the photocatalytic hydrogen evolution of CPs, which could be used for the design and optimization of other photocatalytic systems.