The present study is concerned with the processing and the microstructural analysis of VC/carbon steel surface allayed materials using irradiation of high-energy electron beam. The mixtures of DC powders and flux (50%MgO-50%CaO) were placed on a plain carbon steel substrate, and then electron beam was irradiated on these mixtures using an electron beam accelerator. The microstructures of the irradiated surface layers mere examined by optical microscopy, scanning electron microscopy, and transmission electron microscopy. Residual pores were found in the specimen processed without flux, but hardly found in the specimens processed with a considerable amount of flux. As a result of irradiation, the V content was homogeneously maintained throughout the melted region, and fine vanadium carbides were formed in the melted region. These microstructural modifications including the formation of VC greatly improved hardness, especially high-temperature hardness up to 500℃.