The inhibition effect of dimethylethanolamine(DMEA) and its composite with carboxylic acid was studied with the electrochemical tests. The experimental results indicate that DMEA is not a good inhibitor but the composite of DMEA with caprylic acid exhibits excellent inhibiting efficiency. The synergic mechanism of the organic corrosion inhibitors(OCIs) was studied with quantum chemical calculations. It is found that the DMEA forms a quaternary ammonium salt with the proton in carboxylic acid, and a cyclic complex formed between the salt and Fe may be responsible for the enhancement of inhibiting efficiency. The possible hydrogen bond formed between DMEA and carboxylic acid is not enough for the inhibiting effect. This work is helpful to proposing theoretical interpretation as well as developing a functional organic inhibitor to improve the durability of reinforced concrete contaminated with chloride. The inhibition effect of dimethylethanolamine (DMEA) and its composite with carboxylic acid was studied with the electrochemical tests. The experimental results that that DMEA is not a good inhibitor but the composite of DMEA with caprylic acid exhibits excellent inhibiting efficiency. The synergic mechanism of the organic corrosion inhibitors (OCIs) was studied with quantum chemical calculations. It is found that the DMEA forms a quaternary ammonium salt with the proton in carboxylic acid, and a cyclic complex formed between the salt and Fe may be responsible for the enhancement of inhibiting efficiency The possible hydrogen bond formed between DMEA and carboxylic acid is not enough for the inhibiting effect. This work is helpful to proposing theoretical interpretation as well as developing a functional organic inhibitor to improve the durability of reinforced concrete contaminated with chloride.