AbstractWe demonstrate photovoltaic activity of electrodes composed of fluorine-doped tin oxide (FTO) conducting glass and a multilayer of trimeric photosystem I (PSI) from cyanobacterium Synechocystis sp. PCC 6803 yielding, at open circuit potential (OCP) of + 100 mV (vs. SHE), internal quantum efficiency of (0.37 ± 0.11)% and photocurrent density of up to (0.5 ± 0.1) µA/cm². The photocurrent measured for OCP is of cathodic nature meaning that preferentially the electrons are injected from the conducting layer of the FTO glass to the photooxidized PSI primary electron donor, P700⁺, and further transferred from the photoreduced final electron acceptor of PSI, F_b⁻, via ascorbate electrolyte to the counter electrode. This observation is consistent with preferential donor-side orientation of PSI on FTO imposed by applied electrodeposition. However, by applying high-positive bias (+ 620 mV) to the PSI-FTO electrode, exceeding redox midpoint potential of P700 (+ 450 mV), the photocurrent reverses its orientation and becomes anodic. This is explained by “switching off” the natural photoactivity of PSI particles (by the electrochemical oxidation of P700 to P700⁺) and “switching on” the anodic photocurrent from PSI antenna Chls prone to photooxidation at high potentials. The efficient control of the P700 redox state (P700 or P700⁺) by external bias applied to the PSI-FTO electrodes was evidenced by ultrafast transient absorption spectroscopy. The advantage of the presented system is its structural simplicity together with in situ-proven high intactness of the PSI particles.