Transition metal hydroxides for hydrogen evolution reaction (HER) usually have been limited by poor intrinsic activity and weak conductivity. In our work, in situ electrooxidation as an effective way has been used to modulate the electronic states of active sites for ruthenium hydroxides, which provides obviously enhanced activity for HER in alkaline media. Ag-modified nickel foam (NF) as substrate can provide the excellent conductivity to improve the charge transfer rate of Ru(OH)(x)/Ag/NF. In situ electro-oxidation process has been conducted for Ru(OH)(x)/Ag/NF through OER measurements in alkaline media, which results in the formation of more Ru (IV) as higher actives sites for HER. Compared to Ru(OH)(x)/NF, X-ray photoelectron spectroscopy (XPS) and polarization curves prove that Ag doping in Ru(OH)(x)/Ag/NF may contribute to the oxidization of ruthenium from Ru (III) to Ru (IV) during in situ electro-oxidation. The obtained Ru(OH)(x)/Ag/NF exhibits Pt-like HER activity with a very low overpotential of 103.2 mV to drive 100 mA cm(-2) in 1.0 M KOH. The excellent stability of Ru(OH)(x)/Ag/NF has also been demonstrated. Therefore, our work provides a new strategy by modulating valence state of active sites for transition metal hydroxides for efficient HER. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.