Correlation of microstructure with hardness and wear resistance of VC/carbon steel surface-alloyed materials fabricated by high-energy electron-beam irradiation was investigated. The mixtures of VC powders and flux (50 pct MgO-50 pct CaO or CaF 2 ) were deposited on a plain carbon steel substrate, and subsequently irradiated using a high-energy electron beam. The surface-alloyed layers of 1.2 to 3 mm in thickness were homogeneously formed without defects, and contained a large amount (about 10 vol pct) of VC precipitates in the bainitic or martensitic matrix. This microstructural modification including the formation of hard precipitates and hardened matrix in the surface-alloyed layers improved hardness and wear resistance. Particularly in the surface-alloyed material fabricated with the lower input energy density, the wear resistance was greatly enhanced over the steel substrate because of the increased size and volume fraction of VC particles, although the thickness of the surface-alloyed layer decreased. Microstructural modifications including melting, solidification, precipitation, and phase transformation of the surface-alloyed layer were also predicted from a thermal transfer modeling and a Fe-V-C ternary phase diagram. The predicted results were found consistent with those data from actual electron-beam irradiation and microstructural analysis.