In the present study, the methods of optical, scanning electron, and transmission electron microscopy as well as X-ray diffraction analysis gained insights into the mechanisms of surface finish and microstructure formation of Ti–6Al–4V parts during an EBF³-process. It was found that the slip band propagation within the outermost surface layer provided dissipation of the stored strain energy associated with martensitic transformations. The latter caused the lath fragmentation as well as precipitation of nanosized β grains and an orthorhombic martensite α″ phase at the secondary α lath boundaries of as-built Ti–6Al–4V parts. The effect of continuous electron beam post-treatment on the surface finish, microstructure, and mechanical properties of EBF³-fabricated Ti–6Al–4V parts was revealed. The brittle outermost surface layer of the EBF³-fabricated samples was melted upon the treatment, resulting in the formation of equiaxial prior β grains of 20 to 30 μm in size with the fragmented acicular α′ phase. Electron-beam irradiation induced transformations within the 70 μm thick molten surface layer and 500 μm thick heat affected zone significantly increased the Vickers microhardness and tensile strength of the EBF³-fabricated Ti–6Al–4V samples.