A photoelectrochemical signal chain sensitive to the presence of superoxide radicals was developed on the basis of CdSe/ZnS quantum dots which were immobilized on gold electrodes using a dithiol compound. The conditions of photo current generation under illumination have been characterized with respect to the dependence on the applied electrode potential, the wavelength of the light beam and the stability of the measurement. Because of photoexcitation electron-hole pair generation is enforced in the nanoparticles enhancing the conductivity of the quantum dot layer. This was independently verified by impedance measurements. In order to observe direct electron transfer with the redox protein cytochrome c different surface modifications of the quantum dots were investigated-mercaptopropionic acid, mercaptosuccinic acid and mercaptopyridine. Varying superoxide concentrations in solution can be detected by an enhanced conversion of superoxide-reduced cytochrome c and thus by an enhanced photo current at the quantum dot modified electrode. The electrode was found to be sensitive to higher nanomolar concentrations of the radical.