In this paper plasma electrolytic oxidation (PEO) is examined as a potentially beneficial post-deposition treatment for Al-5wt.%Mg coatings deposited onto Ti alloy substrates using Ion Vapour Deposition (IVD), with a view to replacing toxic hexavalent chromate conversion treatments and at the same time enhancing the barrier protection properties of such IVD coatings. The aqueous corrosion behaviour of PEO layers formed on IVD coatings was evaluated by means of potentiodynamic polarisation scans, open circuit potential measurements and electrochemical impedance spectroscopy. Normally, IVD aluminium-based coatings require a post-coat shot peening treatment to densify the coating structure; however it was found that PEO layers could be formed successfully on as-deposited IVD coatings deposited onto Ti alloy substrates, providing a cost effective process to improve corrosion behaviour. PEO treatment provides unique improvements in the corrosion resistance of IVD coatings; the PEO layer possesses effective anticorrosion properties in aqueous environments containing Cl- ions. A more positive corrosion potential, lower corrosion current and increased polarisation resistance were recorded for PEO layers, compared to traditional chromate conversion treatments.