Vapor-phase hydrodeoxygenation (HDO) of anisole over Mo2C catalysts at low temperatures (420-520 K) and ambient pressure showed (1) remarkable selectivity for C-O bond cleavage, giving benzene selectivity >90% among C-6(+) products, (2) high hydrogen efficiency for the HDO reaction as indicated by low cyclohexane selectivity (<9%), and (3) good stability over similar to 50 h. Methane selectivity increased at the expense of methanol selectivity as anisole conversion increased, suggesting that the phenolic C-O bond was cleaved preferentially. The concurrent near half-/zero-order dependence of benzene synthesis rates on H-2/anisole pressure, and the preferential inhibition of benzene synthesis rates upon introduction of CO relative to isotopic HD exchange suggest that catalytic sites for H-2 activation are distinct from those required for the activation of anisole. The involvement of metallic sites on Mo2C catalysts for this reaction was demonstrated by the nearly invariant benzene synthesis rate per CO chemisorption site. (C) 2014 Elsevier Inc. All rights reserved.