Chloride in atmosphere considerably reduces the corrosion resistance of conventional weathering steel containing a small amount of Cr. Ni is an effective anticorrosive element for improving the corrosion resistance of steel in a Cl-rich environment. In order to clarify the structure of the protective rust layer of weathering steel, Cl and Fe K-edge X-ray absorption near edge structure (XANES) spectra of atmospheric corrosion products (rust) formed on Fe, Fe-Ni and Fe-Cr alloys exposed to Cl-rich atmosphere were measured. The Fe K-XANES measurements enable the characterization of a mixture of iron oxides such as rust. The chemical composition of the rust was determined by performing pattern fitting of the measured spectra. All the rust is composed mainly of goethite, akaganéite, lepidocrocite and magnetite. Among these iron oxides, akaganéite in particular is the major component in the rust. Additionally, the amount of akaganéite in the rust of Fe-Ni alloy is much greater than that in rust of Fe-Cr alloy. Akaganéite is generally considered to facilitate the corrosion of steel, but our results indicate that akaganéite in the rust of Fe-Ni alloy is quantitatively different from that in rust of Fe-Cr alloy and does not facilitate the corrosion of steel. The shoulder peak observed in Cl K-XANES spectra reveals that the rust contains a chloride other than akaganéite. The energy of the shoulder peak does not correspond to that of any well-known chlorides. In the measured spectra, there is no proof that Cl, by combining with the alloying element, inhibits the alloying element from acting in corrosion resistance. The shoulder peak appears only when the content of the alloying element is lower than a certain value. This suggests that the generation of the unidentified chloride is related to the corrosion rate of steel.