Generation of photovoltage and photocurrent from ion exchange membranes containing a viologen moiety was examined, cation exchange membranes ion-exchanged with methyl viologen and anion exchange membranes to which a viologen moiety was bonded. After the membrane, swelled with ethylene glycol, had been clamped between two ITO electrodes and sealed, it was irradiated with a xenon lamp. In the case of the cation exchange membranes ion-exchanged with methyl viologen, 155.3 mV of photovoltage was observed immediately after photoirradiation, and the voltage decreased and attained almost a constant value. The photovoltage of anion exchange membranes with the viologen moiety increased very slowly (maximum 81 mV, 405 nA; load resistance 200 K Omega) after beginning the irradiation. However, when the light was irradiated again on the membrane after interruption of the irradiation, almost the same photovoltage was generated immediately after the irradiation. Though the anion exchange membrane showed absorbance only at 320 nm in the UV-VIS spectrum, wavelengths between 300 and 400 nm were active to reduce the viologen moiety of the membrane. This might be due to a polymer effect. On the other hand, the electrical resistance between the ITO electrodes decreased upon photoirradiation because of radical formation. In order to accelerate generation of the voltage, an oxidative agent (ferric ions) or a reductive agent (triethanolamine) was added to the system. The photovoltage was generated immediately after irradiation in both cases. Ferric ions act as an electron acceptor and triethanolamine forms cation radicals in the membrane before the irradiation.