A noble-metal-free molecular catalyst, [Co(dmbp)(3)]Cl-2 (dmbp=4,4(')-dimethyl-2,2(')-bipyridyl) was prepared for photocatalytic H-2 generation. A three-component photocatalytic system was constructed by combination of [Co(dmbp)(3)]Cl-2 as catalyst, Eosin Y as photosensitizer and triethylamine as sacrificial electron donor to give an efficient H-2 generation system under visible-light irradiation (>420nm). The maximum H-2 yield was up to 249.2 turnover number (vs. catalyst) over 2h irradiation under the conditions with catalyst of 4.0x10(-4)M, 10% TEA (v/v), EY2- of 4.0x10(-4)M and pH10 in MeCN/H2O (1:1,v/v). Furthermore, the dynamics behaviors of the photolysis system were also briefly discussed. Copyright (c) 2014 John Wiley & Sons, Ltd.