Photoelectrochemical (PEC) sensing enables the rapid, accurate, and highly sensitive detection of biologically important chemicals. However, achieving high selectivity without external biological elements remains a challenge because the PEC reactions inherently have poor selectivity. Herein, we report a strategy to address this problem by regulating the charge-transfer pathways using polymeric carbon nitride (pCN)-based heterojunction photoelectrodes. Interestingly, because of redox reactions at different semiconductor/electrolyte interfaces with specific charge-transfer pathways, each analyte demonstrated a unique combination of photocurrent-change polarity. Based on this principle, a pCN-based PEC sensor for the highly selective sensing of ascorbic acid in serum against typical interferences, such as dopamine, glutathione, epinephrine, and citric acid was successfully developed. This study sheds light on a general PEC sensing strategy with high selectivity without biorecognition units by engineering charge-transfer pathways in heterojunctions on photoelectrodes.