Molybdenum hemicarbide (Mo2C), which is widely applied in steel and metal ceramics as well as catalysts, was successfully synthesized by using a simple method of reducing MoO2 powders by CO. It was found that the final reduction product was all Mo2C under both isothermal and nonisothermal conditions. However, the reduction mechanisms were significantly different at lower and higher temperatures: at lower temperatures (1070 to 1342 K), reduction of MoO2 to Mo2C followed a one-step reaction (simultaneous reduction and carburization), while at higher temperatures (1423 to 1485 K), MoO2 was first reduced to metallic Mo, and then Mo was carburized to Mo2C. Mo2C particles obtained at higher temperatures contained micrometer-sized surface features which formed during the MoO2 to Mo reduction step.