Understanding charge transfer dynamics and carrier separation pathway is challenging due to the lack of appropriate characterization strategies. In this work, a crystalline triazine/heptazine carbon nitride homojunction is selected as a model system to demonstrate the interfacial electron-transfer mechanism. Surface bimetallic cocatalysts are used as sensitive probes during in situ photoemission for tracing the S-scheme transfer of interfacial photogenerated electrons from triazine phase to the heptazine phase. Variation of the sample surface potential under light on/off confirms dynamic S-scheme charge transfer. Further theoretical calculations demonstrate an interesting reversal of interfacial electron-transfer path under light/dark conditions, which also supports the experimental evidence of S-scheme transport. Benefiting from the unique merit of S-scheme electron transfer, homojunction shows significantly enhanced activity for CO₂ photoreduction. Our work thus provides a strategy to probe dynamic electron transfer mechanisms and to design delicate material structures towards efficient CO₂ photoreduction.