–A mediator for the measurement of a photocurrent generated by intact cells of cyanobacteria immobilized onto the working electrode in an electrochemical cell is described. The efficiency of diaminodurene (DAD) as an electron shuttle between the photosynthetic electron transport chain (PET) within the cells and the electrode was compared with ferrocyanide and p‐benzoquinone. A simple Synechococcus‐carbon‐paste electrode containing DAD as the mediator in the electrode material and the photosynthetic cells immobilized in a polymer matrix was constructed. The device required no addition of further reagents to the bulk solution for the generation of a photocurrent. Using cyclic voltammetry the second‐order rate constant for the reaction of DAD with the PET was determined. Diaminodurene compared favorably with p‐benzoquinone in that the overpotential was reduced to 0.2 V. The deterioration of the PET by the DAD was significantly decreased compared with p‐benzoquinone, resulting in a prolonged lifetime of the electrode. A possible mechanism for the reaction of DAD with the PET is discussed.