Abstract: Atypical cathodic passivating phenomenon occurring at vitreous carbon electrode in the chromic acid solution was observed. At potentials after the cathodic reduction peak of Cr(Ⅵ) the potential sweep shows clear evidence for the formation of a strongly passivating film. It is confirmed that the presence of anions such as Cl^-, NO₃^-, SiF₄^2-, SO₄^2- causes the reactivation of the electrode surface, though another narrow passivating region reappears at potential just prior to metal deposition. The nature of the passivating film was discussed.