WC/WC interface in VC mono-doped WC-10mass%Co submicro-grained hardmetals of was investigated together with WC/Co interface by using HRTEM and XMA. The thickness of V-rich layer and the analytical value of V at WC/WC interface were almost the same as those at WC/Co interfaces. These results, etc., suggested that the V-rich layers at both interfaces were not generated by an equilibrium segregation mechanism in the sintering stage, but generated by a preferential precipitation mechanism during the solidification of Co liquid phase in the cooling stage. Based on this suggestion, we succeeded in developing a nano-grained hardmetal with 100 nm .