In this work, a novel 2D double-layered metal-organic coordination polymer, [Ni-9(Hmna)(2)(mna)(8)(H2O)(10)]center dot(H2O)(11) (1) (H(2)mna=2-mercaPtonicotinic acid), based on a nonanuclear nickel cluster was synthesized to function as an efficient heterogeneous catalyst with an optimized TON of 685.4 for solar-driven H-2 production from water. Both the solar conversion and water utilization were achieved simultaneously in this photocatalytic system. Without the protection of inert atmosphere, the catalyst was still able to produce hydrogen with a TON of 93.5 in air. The influence of oxygen was studied by virtue of cyclic voltammograms (CVs) and UV-vis adsorption spectrum. The active radicals generated in the photocatalytical process were examined by in-situ electron paramagnetic resonance (EPR) experiments which provided solid evidence to support the reductive mechanism. (C) 2016 Elsevier B.V. All rights reserved.