Ni2P nanocrystallines grown on carbon fiber cloth (Ni2P/CFC) was successfully achieved by a facile vapour-phase hydrothermal method. The as-prepared Ni2P/CFC, as an electrocatalyst, exhibited superior electrocatalytic activities toward urea oxidation reaction (UOR) with a potential of 1.42 V (vs. RHE) delivering a current density of 10 mAcm (2) and hydrogen evolution reaction (HER) with overpotentials of 90 and 155 mV at current densities of 10 and 100 mAcm (2) in alkaline media. On this basis, a Ni2P/CFC constructed two-electrode system for high-efficiency H-2 production and simultaneous urea decomposition was therefore established using commercial urea as reaction source. Besides, such two-electrode system as proof of concept study was also evaluated using human urine as urea source for highly efficient H-2 generation with a rate of 0.35 mu M min (1) at an applied potential of 1.48 V, delivering a current density of 10 mA cm (2). (C) 2017 Elsevier Ltd. All rights reserved.