Abstract: Two new mimetics ofFeFe hydrogenase, 1 and 2, were synthesized using Fe(CO)₅ and a thiol-containing ligand in a multi-step reaction. A three-component homogeneous photocatalytic system was then constructed using complexes 1 or 2 as the photocatalyst, erythrosin B sodium salt (EBS-^2-) as the photosensitizer, and triethylamine (TEA) as the electron donor & proton source for hydrogen production. Under optimal conditions of CH₃CN/H₂O solution volume ratio of 1:1, the pH value of 12, and visible light (λ>420 nm) irradiation for 4 h, the maximum hydrogen production was 205.0 μmol. The turn over number (TON) for compound 2 in catalytic conversion is 51.4. The results show that the ligands contain more proton capture sites, which is conducive to the formation of the hydrogen-producing active intermediate H₂-2Fe2S (η²-H₂-Fe^ⅡFe^Ⅰ) species, further improving the hydrogen production activity of the catalyst. The initial transfer of the photogenerated electron from ^1*EBS^2- to complexes 1 and 2 is thermodynamically favorable, whereas the subsequent transfer of the second electron to these catalysts is thermodynamically unfavorable.