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A high corrosion-resistant passivation film with cerium-molybdenum-chromium-nickel ions has been synthesized on plain carbon steel rebar through a chemical transformation method which significantly lowered the pitting susceptibility of the rebar in the chloride-containing concrete environment. The results indicated that the prepared film has a re-passivation self-healing property in a concrete environment with a concentration of 0.1 M NaCl, which is similar to the behavior of 316L stainless steel. The charge transfer resistance increased markedly with the extension of immersion time, reaching 3.70 × 106 Ω cm2 in about 1500 h of immersion (about 10 times of the initial Rt value). The high corrosion resistance mechanism of the film was discussed here in depth.