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 Ce 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, R 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.