This study involves an investigation into the microstructure and electrochemical properties of an additively manufactured Ti–6Al–4V sample fabricated through electron beam melting (EBM). The microstructural variances along both longitudinal and transverse planes with respect to the build direction were studied. The microstructure in planes parallel and perpendicular to the build direction was characterized using optical and scanning electron microscopy, X-ray diffraction, and transmission electron microscopy with energy-dispersive spectroscopy. Microstructural analysis revealed that different segments along the transverse axis were comprised of mainly α-phase with a minor β-phase presence. As the build progressed from the starting point to the end, both phases exhibited an increase in size, accompanied by noticeable segregation of vanadium and iron into the β-phase. Electrochemical behaviour was studied over time using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The film resistance of the commercially available wrought sample was marginally superior to that of the EBM samples. Notably, the film resistance of the EBM-transverse sample displayed a slightly more pronounced improvement with exposure time compared to its longitudinal counterpart.