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Coumarin has been widely found in some prevailing plants. As green biodegradable inhibitors, the corrosion of mild steel (MS) in 1.0 M aqueous HCl was investigated gravimetrically and electrochemically in the presence and absence a recommended dose (200 ppm) of new synthesized Coumarin’s derivatives {HCA-β-Ala (I), HCA-β-Ala-OMe (II), HCA-β-Ala-Hyd (III) and HCA-β-Ala-Gly (IV)}. The corrosion inhibition efficiency was found exceed 95% in the sequence HCA-β-Ala (I) < HCA-β-Ala-OMe (II) < HCA-β-Ala-Hyd (III) < HCA-β-Ala-Gly (IV). Finally, the density function theory (DFT) was applied to investigate the molecular electrostatic potential (MEP) to identify the interaction of the evaluated compounds on the metallic surface.