Three new biomimetic photocatalyts based on [2Fe2S]-Hases model compound, namely {(μ-pdte) [Fe(CO)3][Fe(CO)2L], μ-pdte = μ2-S(CH2)2CH[(CH2)3COOCH3]S-μ2, L = CO(1), L = PPh3(2)}, (μ-pdte) [Fe(CO)3] [Fe(CO) (phen)] (3), have been synthesized and characterized by elemental analysis, spectroscopy and particularly X-ray crystallography crystal structure analysis for 1. Visible-light-driven H2 evolution catalyzed by 1–3 in the presence of EY2− as PS, and TEA as electron donor, the maximum H2 yield of 136.2 μmol(17 TON vs. catalyst 2) is detected at pH 11 with 2 of 4 × 10−4 M, EY2− of 4 × 10−4 M, TEA of 10% (v:v) in CH3CN/H2O (v:v,1:1) after 4.5 h irradiation. After that, the effect of the substituent species of catalyst on H2 evolution, the stability of photo-catalytic system and the probable H2 evolution mechanism are also carefully discussed by CV, fluorescence quenching, fluorescence lifetime et al. The result illustrates 2 has been found to be a potential catalyst for conversion of solar energy to clean hydrogen energy under visible light-driven despite that the H2 evolution activity is not high enough in this stage.