Four novel [2Fe2S] model complexes(1-4) had been synthesized and characterized by IR, 1 HNMR, elemental analysis and single crystal X-ray crystallography (for 2). The key parameters affecting H 2 evolution of title compounds (1-4) were optimized by constructing homogeneous photo-catalytic system consisting of title sample (1-4) as catalyst, erythrosin B sodium salt (EBS 2-) as photo-sensitizer(PS) and triethylamine(TEA) as sacrificial reagent in CH 3 CN/H 2 O solution under the irradiation of visible light. The maximum H 2 evolution was separately 211.4 6.5µmol