A well-defined dimolybdenum carbide (Mo2C) nano-rod with a porous structure is successfully synthesized through facile carburization of anilinium molybdate in hydrogen. As a catalyst for hydrogen evolution reaction (HER), we investigated its electrical conductivity and catalytic activity. It is found that, as a standalone catalyst, MO2C nano-rod shows a competitive performance for catalysing HER in acidic media. A composite catalyst based on Ni impregnated Mo2C nano-rod is further synthesized to investigate its catalytic behaviour and reaction mechanism in alkaline condition. Compared to commercial Mo2C, the enhanced performance of the Mo2C nano-rod could be attributed to its porous structure with small particles as well as its high electrical conductivity. (c) 2014 Elsevier B.V. All rights reserved.