Formation of chlorate (ClO₃⁻) and perchlorate (ClO₄⁻) as by-products in electrooxidation process has raised concern. In the present study, the formation of ClO₃⁻ and ClO₄⁻ in the presence of 1.0 mM Cl⁻ on boron doped diamond (BDD) and Magneli phase titanium suboxide (Ti₄O₇) anodes were evaluated. The Cl⁻ was transformed to ClO₃⁻ (temporal maximum 276.2 μM) in the first 0.5 h on BDD anodes with a constant current density of 10 mA cm², while approximately 1000 μM ClO₄⁻ was formed after 4.0 h. The formation of ClO₃⁻ on the Ti₄O₇ anode was slower, reaching a temporary maximum of approximately 350.6 μM in 4.0 h, and the formation of ClO₄⁻ was also slower on the Ti₄O₇ anode, taking 8.0 h to reach 780.0 μM. Compared with the BDD anode, the rate of ClO₃⁻ and ClO₄⁻ formation on the Ti₄O₇ anode were always slower, regardless of the supporting electrolytes used in the experiments, including Na₂SO₄, NaNO₃, Na₂B₄O₇, and Na₂HPO₄. It is interesting that the formation of ClO₄⁻ during electrooxidation was largely mitigated or even eliminated, when methanol, KI, and H₂O₂ were included in the reaction solutions. The mechanism of the inhibition on Cl⁻ transformation by electrooxidation was explored.