Supersaturated solid solutions of Al and corrosion-resistant alloying elements (M: V, Mo, Cr, Ti, Nb), produced by non-equilibrium processing techniques, have been reported to exhibit high corrosion resistance and strength. The corrosion mechanism for such improved corrosion performance has not been well understood. We present a fundamental understanding of the role of V in corrosion of an Al-V alloy, which will provide a theoretical background for developing corrosion-resistant Al alloys. High-energy ball milling of the elemental powder of Al and V produced an in situ consolidated Al-V alloy, which exhibited high solid solubility of V. The corrosion resistance of Al-V alloy was significantly higher than that of pure Al, which was attributed to the (1) enrichment of V at the passive film/substrate interface, (2) incorporation of V into the passive film, and (3) deposition of V on the iron-containing cathodic particles and therefore, retardation of cathodic reaction.