Developing cost-effective hydrogen-production systems is always appealing in order to satisfy the future energy request. Here, two Co(II)-salen complexes 1 and 2 were firstly introduced into homogeneous photocatalytic hydrogen-evolution systems. Based on these two cobalt complexes, we developed noble-metal-free hydrogen production systems using xanthene dyes [such as Disodium salts of Eosin Y (EY2-), Rose Bengal (RB2-) and Fluorescein (Fl(2-))] as photosensitizers and trimethylamine (TEA) as sacrificial donor. Complex 1 presented the best catalytic performance for hydrogen production with a TON of 319 based on catalyst within 9h irradiation, which is superior to other cobalt complexes in noble-metal-free systems. UV-Vis spectra studies demonstrate that EY2- suffered quick decomposition, especially under the presence of complex 1, which should be responsible for hydrogen-production deactivation. The thermodynamically favorable photo-induced electron transfer from (3)*EY2- to complex 1 was supported by investigations involving fluorescence quenching and cyclic voltammetry studies. However, the immediate color change (within seconds) as the hydrogen production systems exposed under the irradiation indicates that EY2- firstly suffered dehalogenation which functions as the real active dyes. [GRAPHICS] .