In this paper, an Nb alloying layer on a TC4 alloy was fabricated by using high-current pulsed electron beam (HCPEB) irradiation to improve surface performance. X-ray diffraction (XRD), optical microscopy (OM), laser surface microscope (LSM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the phase composition and microstructure of the surface layer. The microhardness, wear tests and corrosion resistance were also examined. The results show that after HCPEB alloying, a Nb-alloyed layer was formed with about 3.6 μm in thickness on the surface of the sample, which was mainly composed of α’-Ti martensite, β-Ti equiaxial crystals, and NbTi4 particles. After HCPEB irradiation, the surface hardness, wear resistance and corrosion resistance of Nb alloying layer on TC4 alloy were improved compared to the initial samples.