In this investigation, chromium (Cr) was adopted as an alloying element on a nickel substrate, and the alloying process was materialized via high-current pulsed electron beam (HCPEB) irradiation. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were also conducted for microstructure characterization. The results showed that after HCPEB irradiation a nanocrystalline Cr-Ni alloying layer was formed and numerous dislocations were generated, resulting in a great deal of diffusion paths for Cr elements. Moreover, properties including hardness, wear and electrochemical performance were significantly improved after HCPEB irradiation, which was mainly due to the formation of the nanocrystalline Cr–Ni alloying layer. In addition, each strengthening mechanism that contributed to the hardness of the HCPEB-irradiated sample was mathematically analyzed, and solid solution strengthening was found to be of great importance.