The metastable pitting corrosion behavior of laser powder bed fusion (LPBF) produced Ti-6Al-4V is still unclear. Therefore, this work investigated the metastable pitting corrosion of LPBF-produced Ti-6Al-4V in Hank’s solution by electrochemical methods. The LPBF-produced sample (dominant by α′ phase in the microstructure) shows a higher frequency of pit nucleation than the annealed counterpart (composed by α + β dual phase). The passive films formed on the LPBF-produced sample exhibit a higher flux of oxygen vacancies, resulting in the absorption of more aggressive ions (e.g., Cl-) thereby producing more cation vacancies. The condensation of excessive cation vacancies contributes to the pit nucleation. Display omitted •Laser powder bed fusion (LPBF) produced Ti–6Al–4 V alloy was used as the sample.•Corrosion behavior of the LPBF-produced sample was investigated in Hank’s solution.•The LPBF-produced Ti-6Al-4 V shows frequent metastable pitting corrosion.•The flux of oxygen vacancy is large in the passive film of LPBF-produced Ti-6Al-4 V.•Redundant vacancies assemble and condense into a void at metal/film interface.