This work investigates the mechanisms of the microstructure evolution in the melted surface layers of a WC-6% Co hard alloy when increasing the number of pulses of irradiation by high-current pulsed electron beam (HCPEB) treatment. After one pulse of irradiation, about 50% of the stable hcp WC phase was melted and resolidified into the metastable fcc form (WC1−x). When increasing the numbers of pulse irradiation, the WC phase decomposed into ultrafine-grained WC1−x plus nanosized graphite under our selected energy condition. Because of the rapidity of HCPEB carried under vacuum, the formation of the brittle W2C phase was avoided. In the initial Co-rich areas, where the Co was evaporated, melting and solidification led to the formation of nanostructures Co3W9C4 and Co3W3C. The volume fraction of the nano domains containing WC1−x, Co3W9C4, and Co3W3C phases reached its maximum after 20 pulses of irradiation. The improved properties after 20 pulses are therefore due to the presence of nano graphite that served as lubricant and dramatically decreased the friction coefficient, while the ultrafine-grained carbides and the nano domains contribute to the improvement of the surface microhardness and wear resistance.