Abstract— Methyl viologen was reduced by EDTA and other organic compounds when aqueous solutions of these compounds were irradiated near 440 nm in the presence of catalytic quantities of proflavin. The photoreduced methyl viologen was readily oxidized in the dark by the enzyme hydrogenase or platinum asbestos. When the entire reaction was run in the light with hydrogenase or platinum, continuous production of hydrogen was observed. The yield of hydrogen was approximately stoichiometric to the EDTA present establishing that methyl viologen and proflavin were acting catalytically. To establish the structural requirements of the electron donor, eighty compounds were tested at seven pH values between 4 and 10. Of these, twenty served as electron donors for the photoproduction of hydrogen. The effective donors contained either a secondary or tertiary nitrogen atom with one or more carboxymethyl or β‐hydroxyethyl groups, or a sulfhydryl group. The system could also reduce benzyl viologen but not methylene blue. Riboflavin did not replace proflavin for the photoproduction of hydrogen, This system may have potential for producing hydrogen with solar energy. Copyright © 1979, Wiley Blackwell. All rights reserved