The remarkable activity combined with the chemical stability of the PCOFs make them promising candidates for long-term solar-driven photocatalysis experiments, marking a significant step towards practical applications. For the first time, we conducted continuous eight-day experiments on PCOF-1-5, observing steady photostability across all COFs with no substantial decline in catalytic performance (Simulated Sunlight driven photocatalytic set up, Supplementary Fig. ). The COFs maintained nearly identical performance after the eight-day span, with values of 323, 286, 124, 331, and 300 mmol/g of H2, respectively, for PCOF-1 to PCOF-5 (Fig. ). Almost ∼14 liters of H2 were produced from one COF under sunlight simulator irradiation. Furthermore, a long-term experiment conducted in seawater with PCOF-4 as photocatalyst was conducted and revealed a similar trend in H2 production, displaying only a slight decrease in activity (Fig. ). These findings underscore the promising performance of these photocatalysts for practical applications.