The iron rust phase has been analyzed by using EPMA, TEM and EIS after simulating marine corrosion tests. The ultrafine grained (UFG) weathering steel containing Si and Al showed higher corrosion resistance than carbon steel in the test. Si and Al were identified as Si 2+ and Al 3+ in the complex oxide of inner rust by EPMA and TEM. It was demonstrated by EIS that the resistance at the low frequency region corresponded to that of corrosion reaction of rusted steels (Rt). The Rt value of this steel increased after the continuous formation of inner rust, which implied that Si and Al took part in the conversion of complex oxides into fine structure that prevented the penetration of Cl ions.