This work shows that photocatalytic hydrogen evolution from water by microporous organic polymer (MOP)-based photocatalysts can be enhanced by the incorporation of afterglow phosphorescent materials (AG). The photocatalytic MOPs were introduced on the surface of AG through the Stille coupling of tris(4-trimethylstannylphenyl)amine with 3,7-dibromodibenzothiophene sulfone. The resultant AG–MOP–TADS–Pds showed enhanced photocatalytic activities by 2.4 times, compared with MOP–TADS–Pd, due to the Förster resonance energy transfer or charge transfer between AG and MOP–TADS–Pds.