We report the synthesis and corrosion inhibition performance of two imidazole‐based materials, 1,1′‐(4‐methyl‐1,3‐phenylene)bis(3‐(3‐(1H‐imidazol‐1‐yl)propyl)urea) (PIP) and 1,1′‐(hexane‐1,6‐diyl)bis(3‐(3‐(1
H‐imidazol‐1‐yl)propyl)urea) (HIP) dimers, in 1.0 M HCl. Electrochemical assessments indicated that the synthesized dimers facilitated the formation of a protective layer at the metal‐electrolyte interface and, as a result, blocked the active corrosion sites. At a concentration of 100 ppm, PIP behaved as a potential mixed‐type anticorrosive material with an overall efficiency of 99%. Density functional theory calculations showed that the aromaticity existing in the PIP backbone plays a major role in facilitating the corrosion‐inhibition role.