Step-scheme heterojunctions formed between two firmly bound photocatalysts facilitate charge separation due to interfacial charge transfer, which is usually illustrated by the gain or loss of electrons in the constituent photocatalysts characterized by in situ irradiated X-ray photoelectron spectroscopy. This technique provides a steady-state view of charge distribution but overlooks the transient and complex dynamics of charge transfer, trapping, and recombination. To provide a molecular-level and dynamic view of these processes, we investigated the behaviors of photogenerated charge carriers within an inorganic/organic TiO2/polydopamine S-scheme heterojunction using ultrafast transient absorption spectroscopy and time-resolved photoluminescence spectroscopy. We found the interfacial charge transfer within the step-scheme heterojunction occurred at a smaller shorter time scale than recombination, leading to efficient charge separation. Moreover, the charge-discharge property of polydopamine induces electron backflow, which should be avoided in practical photocatalytic applications. The composite showed higher photocatalytic H2O2-production activities due to faster H2O2 formation and suppressed H2O2 decomposition.