The objective of this study is to investigate the ballistic properties of Zr-based amorphous alloy surface composites fabricated by high-energy electron-beam irradiation. The mixture of Zr-based amorphous powders and LiF+MgF2 flux powders was deposited on a pure Ti substrate, and then an electron beam irradiated this powder mixture to fabricate a one-layer surface composite. A four-layer surface composite, in which the composite layer thickness was larger than 3 mm, was also fabricated by irradiating the deposited powder mixture by an electron beam three times on the one-layer surface composite. The microstructural analysis results indicated that a small amount of fine crystalline particles were homogeneously distributed in the amorphous matrix of the surface composite layer. According to the ballistic impact test results, the surface composite layers effectively blocked a fast traveling projectile, while many cracks were formed at the composite layers, and thus the surface composite plates were not perforated. The surface composite layer containing ductile β dendritic phases showed a better ballistic performance than the one without dendrites because dendritic phases hindered the propagation of shear bands or cracks.