Steel rebars with oxide scale, which is usually rich of defects, are widely used in industry. On the surface of the oxide scale, it is difficult to prepare a conversion film with desirable corrosion resistance because of the acidity of conventional conversion solutions. In this work, a sol–gel solution (pH = 11) was employed to retard the diffusion of cerium ions avoiding the formation of cerium salt precipitates at room temperature. After treatments, the diffusion of cerium ions would be accelerated and a protective conversion film would form to repair natural defects on oxide scale of steel rebars at a higher temperature. This strategy can not only avoid the peeling of the oxide scale by the acid solution, but also prevent a large amount of non-uniform precipitation of the film-forming Ce3+ ions. The conversion film@oxide scale was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curve (PPC) etc. It is found that the corrosion resistance of the prepared film@oxide scale was enhanced greatly when the concentration of added cerium ion (III) was 0.5 M, with pH adjusted to 11. After 30 days of immersion, Rct of surface treated rebar is more 180 times that of blank sample. The excellent corrosion resistance is closely related to the double-layer structure of the prepared sol-gel film, especially an about 2 nm inner layer of cerium oxide.