Developing photocatalysts to steer conversion of solar energy toward high-value-added fine chemicals represents a potentially viable approach to address the energy crisis and environmental issues. However, enablement of this conversion is usually impeded by the sluggish kinetic process for proton-coupled electron transfer and rapid recombination of photogenerated excitons. Herein, we report a simple and general structural expansion strategy to facilitate charge transfer in conjugated microporous polymers (CMPs) via engineering the donor surrounding the trifluoromethylphenyl core. The resulting CMPs combine high surface area, strong light-harvesting capabilities, and tunable optical properties endowed by extended π-conjugation; the optimized compound CbzCMP-5 generated from 9,9′,9″-(2-(trifluoromethyl)­benzene-1,3,5-triyl)­tris­(9H-carbazole) remarkably enhanced the photogenerated carrier transfer efficiency, enabling the functionalization of thiophenols toward thiocarbamates and 3-sulfenylindoles with high photocatalytic efficiency. Most importantly, the in-depth insights into the carrier-transfer processes open up new prospects on further optimization and rational design of photoactive polymers for efficient charge-transfer-mediated reactions.