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Using an environmentally friendly acid-alcohol system solution for electrochemical polishing of 3D printed titanium alloy, a typical U-I polarization curve was obtained, and explained the mechanism of electrochemical polishing. In this paper, the influence of electrochemical polishing factors (electrolyte temperature, polishing distance, and polishing time) on the surface roughness of Ti-6Al-4V (TC4) was studied, and optimized the process parameters to obtain a surface roughness of 0.3 μ m (1 mm × 1 mm). Electrochemical polishing can reach the level of mechanical grinding and polishing, meeting the requirements for subsequent assembly and use.