Designing S-scheme heterojunctions with enhanced interfacial interaction is an effective strategy for promoting the separation of photocarriers while maintaining strong photoredox capabilities. However, precisely tailoring the interfacial charge transport pathways between two contacted semiconductors remains a significant challenge due to the similar band alignment in type-II and S-scheme heterostructures. Herein, we report a facile and low-cost carbon doping strategy to smartly tune the charge transfer pathway via a type-II to S-scheme transformation for efficient photocatalytic H2 evolution and H2O2 synthesis. Density functional theory calculations combined with in situ XPS studies demonstrate that the Fermi level of MoO2 shifts from being higher than that of C3N4 to being lower after carbon doping, which drives the inversion of the internal electric field (IEF) direction between MoO2 and C3N4, thus enabling a transition from type-II MoO2/C3N4 heterojunctions to S-scheme C-MoO2/C3N4 heterojunctions. As a result, the optimal S-scheme C-MoO2/C3N4 heterojunctions exhibit a high H2 evolution rate of 16.2 mmol g-1 h-1 and a H2O2 production rate of 877 μmol g-1 h-1, notably surpassing those of the original C3N4 and type-II MoO2/C3N4 heterojunctions. This work provides valuable insights into the fabrication of C3N4 heterostructures and the control of electron migration pathways, thereby creating new possibilities for photocatalysis and optoelectronics applications.