Coordination of the pyridyl-attached diiron azadithiolate hexacarbonyl complexes (2 and 3) through the pyridyl nitrogen to the Re on 10-phenanthroline rhenium (5a) and 2,9-diphenyl-1,10-phenanthroline rhenium (5b) forms novel [Re–Fe] complexes 7a, 7b and 8 respectively. Under visible light illumination using triethylamine as a sacrificial electron donor and [Re–Fe] type complexes (7a, 7b or 8) as catalysts, remarkably increased efficiency was observed for photoinduced hydrogen production with a turnover number reaching 11.8 from complex 7a and 8.75 from 7b. To the best of our knowledge, these are the best values compared to other [Re–Fe] photocatalysts reported so far. In contrast to the parent molecules, the turnover number by the intermolecular combination of complexes 6a and 2 showed a value of 5.23, and that from 6b and 2 is 3.8, while no H₂ was detected from 8a and 3 under the same experimental conditions. Obviously, the intramolecular combination of rhenium(I) and [2Fe2S] as a catalyst is promising for efficient H₂ evolution, and it is better than the intermolecular multi-component system.