In summary, we have synthesized a series of highly active hydrogen evolution polymer photocatalysts that contain sulfur and boron moieties (SBPs), and in doing so, we introduced a readily available electron acceptor, triarylborane, to the library of building blocks for visible-light photocatalysts. Under optimized conditions, the thieno[3,2-b]thiophene-triarylborane copolymer (TT-TAB) produces 113.9 mmol of hydrogen per hour per gram of catalyst. Most importantly, even without added platinum co-catalyst, its activity is close to 100 mmol h -1 g -1 , a benchmark value. These findings emphasize the importance of donor-acceptor dyads for effective separation and utilization of photoexcited charge carriers in efficient photocatalytic processes.