We report a facile hydrothermal synthesis of nanorod-structured molybdenum-tungsten oxides as an efficient catalyst for olefin hydrogenation. The catalytic activity was demonstrated through hydrogenation of cyclohexene used as a model system. The as-prepared material was confirmed as a new phase (Mo0.6W0.4O3) via a series of characterizations, instead of a simple mixture of MoO3 and WO3. The Mo0.6W0.4O3 catalyst displays excellent catalytic activity with 100% conversion of cyclohexene in 3 h, which is much higher than that of pure MoO3 and pure WO3 synthesized with the same method. It was found that hydrogen bronze (HxMo0.6W0.4O3) was formed during the hydrogenation process, and the catalytic performance was positively correlated with the hydrogen content. The obtained nanorod-structured Mo0.6W0.4O3 without loading any noble metal exhibits much higher catalytic activity than a Pd/MoO3 catalyst. The results demonstrate that the nanorod-structured molybdenum-tungsten oxide may be a strong contender for serving as an efficient hydrogenation catalyst alternative to precious metals.