Solar hydrogen generation from water represents a Compelling component of a future sustainable energy portfolio. Recently, chemically robust heptazine-based polymers known as graphitic carbon nitrides (g-c(3)N(4)) have emerged as promising photocatalysts for hydrogen evolution using-visible light while withstanding harsh chemical environments. However, since g-C3N4 electron-transfer dynamics are poorly understood, rational design rules for improving activity remain unclear. Here, we use visible and near-infrared femtosecond transient absorption (TA) spectroscopy to reveal an electron-transfer cascade that correlates with A near-doubling in photocatalytic activity from 2050 to 3810 mu mol(-1) g(-1) when we infuse a suspension of bulk g-C3N4 with 10% mass loading of chemically exfoliated carbon nitride. TA spectroscopy indicates that exfoliated carbon nitride quenches photogenerated electrons on g-C3N4 at rates approaching the molecular diffusion limit. The TA signal for photogenerated electrons on g-C3N4 decays with a time constant of 1/k(e)' 660 ps in the mixture versus 1/k(e) = 4.1 ns in g-C3N4 alone. Our TA measurements suggest that the charge generation efficiency in g-C3N4 is greater than 65%. Exfoliated carbon nitride, which liberates only trace hydrogen levels when photoexcited directly, does not appear to, independently sustain appreciable long-lived charge generation. Thus, the activity enhancement in the two-component infusion evidently results from a cooperative effect in which charge is generated on g-C3N4, followed by electron transfer to exfoliated carbon nitride containing photocatalytic chain terminations. This correlation between electron transfer and photocatalytic activity, provides new insight into structural modifications for controlling charge separation dynamics and activity of carbon-based photocatalysts.