In this work, we show a new application of Brønsted PAs and PBs for light-driven photoelectrochemical photocurrent generation. We demonstrate that the ESPT of PAs and PBs can be utilized for photocurrent production and polarity switching in an electrochemical cell, both in single-cell and H-cell configurations. Unlike common photoelectrochemical devices for photocurrent generation, the use of PAs and PBs results in a fundamentally different mechanism for photocurrent generation. In common photoelectrochemical cells, photocurrent generation is a result of an electron transfer process between the electronically excited state and the electrode. In the system presented here, the photocurrent generation is due to an ESPT process. While the goal of this work is to introduce a new mechanism for harvesting light in photoelectrochemical cells, the new knowledge discussed here can be utilized in future devices, either for photocurrent generation or for energy storage.