The microstructure of double-sided welded joints of 3D-printed items made of titanium alloy Ti‒6Al–4V by the electron-beam freeform fabrication (EBF3) method has been investigated using the methods of X-ray diffraction analysis, optical metallography, and scanning and transmission electron microscopy. It is found that columnar epitaxial growth of primary β grains with transverse dimensions close to the sizes of primary β grains in the base material occurs in the process of electron-beam welding with a double-sided welded joint. Inside the primary β grains, there are grains of the α-phase with a lamellar shape inherited from the α' martensite, which is formed in the course of transformation β → α'. As in the printed samples, there is a nanocrystalline α"-phase in the metal of the welded joint inside grains of the α-phase and in interlayers of the β-phase. However, the density of particles of this phase in the metal of the welded joint is higher than in the base material. In the metal of the welded joint, tensile macrostresses and elastic residual microstrains also increase. The microhardness of the metal of the welded joint is greater than the microhardness of the base material.