Controlling the activity and selectivity of hydrodeoxygenation (HDO) of biomass-derivatives is critical for the utilization of biomass as renewable sources for chemicals and fuels. Furfural, produced by the hydrolysis and dehydration of xylose from hemicellulose, is a promising biomass-derivative to produce important biofuels like 2-methylfuran. Using a combination of density functional theory (DFT) calculations and surface science measurements on Fe/Ni(111) model surfaces, our results indicate that furfural bonds to the bimetallic surfaces primarily through the C=O bond with the furan ring tilted away from the surface, leading to the production of 2-methylfuran through the HDO reaction with furfuryl alcohol being identified as the likely intermediate. Similar preferential interaction of the C=O group over the furan ring is also confirmed on SiO2-supported FeNi bimetallic catalysts. The similar trends observed on model surfaces and supported catalysts demonstrate the feasibility of using single crystal surfaces to identify precious-metal-free bimetallic catalysts for biomass conversion. (C) 2014 Elsevier Inc. All rights reserved.