Exciton binding energy has been regarded as a crucial parameter for mediating charge separation in polymeric photocatalysts. Minimizing the exciton binding energy of the polymers can increase the yield of charge‐carrier generation and thus improve the photocatalytic activities, but the realization of this approach remains a great challenge. Herein, a series of linear donor–acceptor conjugated polymers has been developed to minimize the exciton binding energy by modulating the charge‐transfer pathway. The results reveal that the reduced energy loss of the charge‐transfer state can facilitate the electron transfer from donor to acceptor, and thus, more electrons are ready for subsequent reduction reactions. The optimized polymer, FSO‐FS, exhibits a remarkable photochemical performance under visible light irradiation.