Hydrogen evolution reaction (HER) is considered to be one of the most promising strategies to create hydrogen. Recently, searching high-efficient, stable, and earth-abundant electrocatalysts to replace precious metals for practical utilizations of HER is attracting more and more attentions. Herein, novel molybdenum carbide nanobelts containing Mo of high-valence state derived from MoO3-ethylenediamine inorganic/organic hybrid precursors are successfully synthesized via a facile one-pot pyrolysis method. The molybdenum carbide nanobelts are characterized using XRD, SEM, TEM and XPS. Moreover, the high-valence state Mo and their relative content in the molybdenum carbide nanobelts can be identified by XPS. The high-resolution XPS spectra of Mo 3d indicates in the molybdenum carbide nanobelts the proportion of high-valence state Mo in active Mo components is 51.3%. More importantly, the as-synthesized products exhibit excellent electrocatalytic activity for HER with a low onset overpotential of 50 mV and a small Tafel slope of 49.6 mV dec(-1) in acidic medium (0.5 M H2SO4). Besides, the catalysts require only overpotentials of 143 and 234 my to achieve current densities of 10 and 220 mA cm(-2), respectively. Furthermore, they also exhibit good durability after 2000 cycles and constant current density test. Such excellent electrocatalytic HER performance can be ascribed to the high intrinsic activity of high valence state Mo in Molybdenum Carbide. Synthesizing molybdenum carbide with high valence state Mo electrocatalysts for HER will open up an exciting alternative avenue to acquire outstanding HER electrocatalytic activity. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.