This study is aimed to evaluate the effect of concentrated benzimidazole (BIM) on the cathodic disbonding (CP) of an epoxy coating applied on steel substrate. For this purpose, the polymeric coatings, formulated with different concentrations of BIM (0 wt.%, 0.5 wt.%, 0.75 wt.%, and 1 wt.%, were subjected to the CP test at the potential of −1.2 V vs. Ag/AgCl during 24 h immersion in 3.5 wt.% NaCl solutions. The optimum formulation was found through taking advantage of the CP test results, FESEM/EDX, and EIS data. Moreover, a pull-off test was used to measure the wet adhesion strength. For insight into the inhibition function of the organic inhibitor, the behavior of steel in the sodium chloride solutions, with and without BIM, was compared using EIS and surface analysis.