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Electrochemical corrosion behaviours of vanadium and V-5Cr-5Ti alloy in chlorine ion solution have been studied by electrochemical techniques. The results indicate that in 50 μg/g Cl- potassium chloride solution, corrosion potential of vanadium is higher than that of V-5Cr-5Ti alloy, and therefore vanadium is more stable in thermodynamics. Relative to V-5Cr-5Ti alloy, vanadium has much higher polarization resistance and even lower corrosion current. Vanadium and V-5Cr-5Ti alloy have similar cathodic polarization behaviour. In the process of anodic polarization, vanadium manifests Tafel behaviour mainly and V-5Cr-5Ti alloy represents “pseudo-passivation” and passivation behaviours. They have negative cyclic polarization hysteresis loop. Corrosion resistant performance of vanadium is better than that of V-5Cr-5Ti alloy.