Steam reforming of methanol over nanostructured wire-like molybdenum carbides, which were synthesized by direct carburization of aniline-intercalated molybdenum based organic-inorganic hybrid composite at different temperatures, were investigated in details. SEM and TEM images revealed that the obtained wire-like molybdenum carbide was composed of nano-particles (10-20 nm) and had microporous structure. These wire-like molybdenum carbides showed higher catalytic activity than those synthesized via the conventional temperature programmed reaction (TPRe) method. It is found that the wire-like molybdenum carbide synthesized at 675 C had higher surface area (93.2 m(2)/g) and showed more excellent catalytic activity and longer term stability. XRD results indicated that more alpha-MoC1-x, phase existed in this kind of molybdenum carbide. It indicated that an alternative high-performance molybdenum carbide catalyst can be easily obtained by adjusting the synthesis condition. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.