Benzotriazole (BTA) release from a layered double hydroxide based on Zn and Al (LDH-ZnAl/BTA) in a saline solution was investigated using UV-Vis spectroscopy, and corrosion protection was studied by OCP and EIS measurements on carbon steel samples immersed in 3.5 wt-% NaCl solution. The corrosion protection of this ion-exchanger material performance for longer periods was evaluated using a carbon steel substrate coated with a commercial epoxy primer loaded with LDH-BTA (5.0 wt-%). EIS and salt spray tests demonstrated that the LDH-BTA additive enhanced the performance of the commercial primer due to the double inhibitive effect, which is a combination of the entrapment of chloride anions simultaneously with the on-demand release of the corrosion inhibitor BTA.