Donor-acceptor (D-A)-type photocatalysts containing the polycyclic aromatic donor (BTT-CPP) and non-polycyclic aromatic donor ( TTB-CPP) are designed and synthesized. Their physicochemical properties are thoroughly investigated. The photocatalytic hydrogen generation experiments show that both polymers exhibit distinct photocatalytic performance. BTT-CPP displays an attractive hydrogen evolution rate (HER) of 37,866 mu mol g(-1) h(-1) without further addition of the metal co-catalyst, one of the highest values reported for organic photocatalysts. The optimal HER of TTB-CPP is 8466 mu mol g(-1) h(-1). These results highlight the important role of the donor unit on the performance of D-A-type photocatalysts and demonstrate that thiophene-contained polycyclic aromatic unit BTT is an excellent donor unit for high HER photocatalysts.