Although the corrosion properties of Ti-6Al-4V have been widely studied, the differences in passive film evolution and corrosion mechanism between wrought and SLMed Ti-6Al-4V in acidic service environments are still unclear. In this work, the corrosion behaviors of wrought and selective laser melting (SLMed) Ti-6Al-4V alloys in 0.05 mol/L H₂SO₄ solution were systematically investigated using electrochemical impedance spectroscopy, potentiodynamic polarization curves, Mott–Schottky analysis and XPS depth profiling. Wrought and SLM-fabricated Ti-6Al-4V were selected to reveal the effects of typical forming processes on corrosion resistance, considering their wide applications and distinct microstructures. Electrochemical results demonstrate that the wrought alloy exhibits a higher polarization resistance, a thicker passive film, and a lower corrosion current density, corresponding to superior corrosion resistance. Mott–Schottky analysis reveals that the passive films formed on both alloys show n-type semiconductor characteristics, while the wrought alloy possesses a lower carrier concentration, fewer defects, and a more compact film structure. XPS depth analysis indicates that the content of TiO₂ in the passive films decreases with increasing etching depth, accompanied by an increase in TiOOH, TiO, and metallic Ti.