In this work, the effects of mechanical milling on the extent of reduction were investigated to give an overview of potential improvements in the preparation of WC. A mixture of graphite and tungsten oxide (WO3) was mechanically milled together for 10 h. The as-milled powder and un-milled powder were investigated by thermal analysis, isothermal treatment, and X-ray diffraction to determine the effect of milling on the carbothermal reduction of WO3 to tungsten carbide (WC). The as-milled powder underwent a rapid reduction reaction at about 150°C lower than the un-milled powder. The reduction sequence to WC was illustrated to differ for the two powders. The milled powder showed complete reduction to WC in 1 h at 1215°C whereas the un-milled powder was incompletely reduced. Finally, WC powder was readily achieved by carbothermic reduction of mechanical activated WO3 and graphite, leaving its grains nano-sized.