In this present paper, the electropolishing behavior of Ti–6Al–4V alloy fabricated by additive manufacturing in chloridecontainingethylene glycol electrolyte was surveyed. The impacts of chloride ion on surface quality and oxide film ofTi–6Al–4V were analyzed in dependence on the surface topography, roughness, weight loss ratio and compositions. Thevisual and microscopic results revealed that the optimally electropolished surface was attained in a 0.4 mol L−1 chlorideelectrolyte with a decreased surface roughness of 75.04% and a weight loss rate of 4.93%. For lower (CCl−1 ≤ 0.3 mol L−1)or higher concentrations (CCl−1 ≥ 0.5 mol L−1), a smooth and flat surface was not observed due to insufficient reactions orexcessive anodic dissolution. During the electropolishing, the titanium oxides nucleated and corresponding surface tensionincreased, resulting in the formation of a stable TiO2film on the surface of the Ti–6Al–4V alloy, increasing the corrosionresistance of the specimen.