Synthesis of liquid fuels (C hydrocarbons) via CO hydrogenation is very promising. Hydrogenation of CO to liquid hydrocarbons usually proceeds through tandem catalysis of reverse water gas shift (RWGS) reaction to produce CO, and subsequent CO hydrogenation to hydrocarbons via Fischer-Tropsch synthesis (FTS). CO is a thermodynamically stable and chemically inert molecule, and RWGS reaction is endothermic and needs a higher temperature, whereas FTS reaction is exothermic and is thermodynamically favored at a lower temperature. Therefore, the reported technologies have some obvious drawbacks, such as high temperature, low selectivity, and use of complex catalysts. Herein we discovered that a simple Co/MnO nanocatalyst could efficiently catalyze CO hydrogenation. The reaction proceeded at 200 °C, which is much lower than those reported so far. The selectivity of liquid hydrocarbon (C to C, mostly -paraffin) in total product could reach 53.2 C-mol%, which is among the highest reported to date. Interestingly, CO was hardly detectable during the reaction. The in situ Fourier transform infrared characterization and CO labeling test confirmed that the reaction was not via CO, accounting for the eminent catalytic results. This report represents significant progress in CO chemistry and CO transformation.