A new catalyst based on a cobalt complex [LCoCl] I is formed by the reaction of dimethylaminoethylamino-N,N-bis(2-methylene-4-tert-butyl-6-methyl) phenol (H2L) with CoCl2 center dot 6H(2)O for both electrolytic and photolytic water reduction. 1 can electrocatalyze hydrogen evolution from water with a turnover frequency (TOF) of 230 moles of hydrogen per mole of catalyst per hour at an overpotential of 689 mV (pH 7.0). Additionally, under photoirradiation with blue light (lambda(max) = 469 nm), 1, together with [Ru(bpy)(3)]Cl-2 and ascorbic acid in a pH 6.0 aqueous solution, also produces hydrogen with a remarkable turnover number (TON) of 4130 mol of H-2 per mol of catalysts. This performance is different from the reported results that the best pH for photocatalytic H-2 evolution by photo-catalyst was observed at pH 4.0. This discovery has established a new chemical paradigm for creating water reduction catalyst that is highly active near neutral media. (C) 2015 Elsevier B.V. All rights reserved.