The main perspective of this paper is to prepare an eco-friendly corrosion inhibitor suitable for reinforced concrete. The properties of CaAl-LDHs loaded with ethylenediaminetetraacetic acid (EDTA) synthesized under different conditions were studied and the optimal condition was determined. Electrochemical tests showed that CaAl-EDTA-LDH had excellent anti-corrosion properties for steel bars in the simulated concrete pore (SCP) solution. Mechanistically, the dual protection mechanism of CaAl-EDTA-LDH on steel bars was mainly due to the fact that the organic corrosion inhibitor adsorbed on the surface of steel bars to form a protective film while consolidating chlorides.