Four novel [2Fe2S] model complexes (1-4) had been synthesized and characterized by IR, H-1 NMR, 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 compounds (1-4) as catalyst, erythrosin B sodium salt (EBS2-) as photo-sensitizer (PS) and triethylamine (TEA) as sacrificial reagent in CH3CN/H2O solution under the irradiation of visible light. The maximum H-2 evolution was separately 211.4 +/- 6.5 mu mol (52.9 +/- 1.6 TON vs. 4), 199.4 +/- 13.5 mu mol (49.9 +/- 3.4 TON vs. 1), 124.8 +/- 7.6 mu mol (31.2 +/- 1.9 TON vs. 3) and 34.9 +/- 6.9 mu mol (8.7 +/- 1.7 TON vs. 2) under the optimal conditions with catalyst of 2 x 10(-4) mol.L-1, EBS2- of 4 x 10(-4) mol.L-1, TEA of 10% (v/v) and pH 12 in CH3CN/H2O (1/1, v/v) solution. Furthermore, the structural effect and mechanism of electron transfer in the present system was carefully discussed by fluorescence spectra and cyclic voltammetry (CV) measurements. (C) 2016 Elsevier Ltd. All rights reserved.