“…To date, various PEC sensors have been well-documented, such as bioanalysis-based and direct reactant-determinant PEC sensors. ,,– While the bioanalysis-based PEC biosensors employ biological elements (e.g., enzymes, antibodies, and nucleic acids) for highly specific recognition, ,– the direct reactant-determinant PEC sensors are a straightforward approach on the basis of redox reactions between the analytes and excited carriers of the photovoltaic materials. – Nonetheless, direct reactant-determinant PEC sensors receive relatively less attention owing to poor selectivity . In principle, regulating charge-transfer pathways would tune the redox reactions, which generate diverse and even opposite photocurrent changes in response to analytes, thus offering an intriguing way to improve the detection selectivity. , Interestingly, task-specific charge-transfer pathways could be modulated by orderly assembling different photovoltaic materials with suitable CB and VB positions, e.g., through the Z-scheme and Type II heterostructures (Figure d,e). ,– From the perspective of signal transduction, except for conventional endeavors in improving PEC efficiency for more sensitive detection, engineering charge-transfer pathways would play an essential role in selective PEC sensing, but to the best of our knowledge, it has been rarely reported …”