K, Mg, and Ca modified nanowire molybdenum carbide have been prepared using an organic-inorganic hybrid method for the production of higher alcohols and hydrocarbons from the hydrogenation of CO. The results revealed that unpromoted molybdenum carbide mainly produced light alkanes, and only few alcohols were obtained. The promoters improved selectivity shift from alkane to alcohols in the sequence: K>Mg>Ca. Additional, the CO conversion was reduced with the addition of K and Mg, with K exhibiting more vigorous effect, but that remarkably increased for Mg. Moreover, the promoters showed different effectiveness on the ability of chain propagation. Potassium mainly enhanced the ability of alcohol chain propagation with higher selectivity to C2(+)OH, but had little effect on that of alkane. While, for magnesium and calcium, they mainly improved the ability of alkanes chain propagation with reducing the formation of methane.