In this study, we show the potential of using PAs (2N6S) and PBs (6AQ) in a photoelectrochemical setup for light-induced current generation. By using several electrochemical techniques (CV and CA) acquired before and during the irradiation of the solution in both single-cell and two-compartment H-cell configurations, we observed photocurrent generation and discussed the role of ESPT from/to the PA/PB in the electrochemical process. Our results indicate that the formed ions in the excited state (RO - /H + /RNH + ) have a crucial role in the electron transfer processes involving the WE and CE in both the negative and positive bias regimes. By using a methylated derivative of a photoacid that cannot undergo the ESPT process, we validated that the observed photocurrent generation is not due to the direct sensitization of the electrode by the excited PA. The H-cell configuration allowed to photo-modulate the electrical current intensity and polarity by irradiating a specific half-cell, either the one of the PB or the one of the PA, while the proton-conducting membrane separating the half-cells is serving as a proton pump between the cells. Our study here represents a new concept in photoelectrochemistry and shifts the discussion from purely electronic processes to processes involving proton transfer. The concepts initiated in this study can be further utilized in devices targeting light-responsive energy production, energy storage, and hydrogen formation applications.