A new process of WC-Co cemented carbide was developed by using nano-grained W(Co, C) composite powders as raw materials processed by high-energy ball milling. X-ray diffraetion(XRD), differential thermal analysis (DTA), thermo-gravimetrie (TG) analysis and coercive forces of the sintered samples were adopted to analyze the phase transformation and constitution, and the microstructures of sintered samples were characterized by scanning electron microscopy(SEM). The results show that the as-milled powders are transformed into transitional phases W2C and η (Co3W3C or Co6W6C) during sintering, and finally transformed into WC and Co phases completely at 1 250℃ for 30 min, and a large number of fibrous WC grains with about 1.2μm in length and 100 nm in radial dimension are formed in the sintered body at 1 300 ℃.