Iron–thiolate complexes of the type [Fe2(μ-bdt)(CO)6−xP(OMe3)x] (bdt=S2C6H4=benzenedithiolate, x≤2) are simplified models of iron–iron hydrogenase enzymes. Recently, we have shown that these water-insoluble organometallic complexes, when included into micelles formed by sodium dodecyl sulfate (SDS), are good catalysts for the electrochemical production of hydrogen in aqueous solutions at pH<6. We herein report that the all-CO derivative [Fe2(μ-bdt)(CO)6] (1), owing to its comparatively low reduction potential, is also a robust molecular catalyst for visible-light-driven production of H2 in aqueous SDS solutions at pH 10.5. Irradiation at λ=455 nm of a system consisting of complex 1, Eosin Y as a sensitizer, and triethylamine as an electron donor produced up to 0.86 mL of H2 in 4.5 h, corresponding to a turnover number of 117 mol of H2 per mol of catalyst. In the presence of a large excess of sensitizer, the production of H2 lasted for more than 30 h, stressing the relative stability of complex 1 under the photocatalytic conditions used herein. Thermodynamic considerations and UV/Vis spectroscopy experiments suggest that the catalytic cycle begins with the photo-driven reduction of complex 1. The reduced intermediate reacts with a proton source to yield iron hydride. Subsequent reduction and protonation steps produce H2, regenerating the starting complex. As a result, the iron–thiolate complex 1 is a versatile proton reduction catalyst that can utilize either solar or electrical energy inputs, providing a starting point for the construction of noble metal-free molecular systems for renewable H2 production.