The gas-phase hydrogenation of crotonaldehyde has been performed over unsupported Mo2N and over Mo2N supported on two carbonaceous materials, an activated carbon (AC) and a high surface area graphite (G). These catalysts were in situ prepared by the temperature-programmed reaction of MoO3 and carbon-supported Mo precursors with NH3. It is found that selectivity to the unsaturated alcohol is maximum for the Mo2N/G sample, where crotylalcohol selectivities exceed the 60% during all time in reaction. Higher selectivity surface sites are associated with the (200) planes of the gamma-Mo2N crystallites.