Photoluminescence (PL) spectra of pristine PCOF-1-5 and PCOF-1-5-AA were recorded to give further insight into the charge separation efficiency. The steady-state PL emissions were measured after the COFs were dispersed in water and excited at 370 nm. Emission maxima were observed at 545-600 nm for PCOFs, with a smaller Stokes shift (545 nm) for the fluorine rich PCOF-5 and a larger Stokes shift (600 nm) for PCOF-1 (Supplementary Figs. ). The other three pore hydrophilic COFs showed better intensity with emission at 570 nm. For PCOF-1-5-AA, a significant quenching of fluorescence is observed, with a red-shift of the remaining emission signal (675 nm). Only PCOF-5AA shows very low photoluminescence in the non-and protonated case. Exciton and charge carrier dynamics of PCOFs and PCOF-AA were revealed from time-correlated single-photon counting (TCSPC) (Supplementary Fig. ) The average lifetime (avg) of PCOF-1, 2, 3, 4, and 5 was estimated to be 0.054, 0.029, 0.025, 0.027, and 0.123 ns, however, higher values are seen for PCOF-1AA, 2AA, 3AA, 4AA, and 5AA namely 0.44, 0.32, 0.12, 0.61, and 0.16 ns, respectively, showing an improved charge separation dynamic for PCOF-AAs compared to PCOFs.