The development of highly stable coatings on iron is essential for mitigating corrosion formation. Herein, it is demonstrated that a self-assembled monolayer of N-Heterocyclic Carbene (NHC) can be electrodeposited on iron foil and function as a binder for a secondary, crosslinked polymer network coating. The dual layer coating, constructed of a monolayer of NHCs and a polymer film, as a primary and a secondary coating, respectively, effectively preventes corrosion formation with a protective efficiency of 99.6 ± 0.2 %, as determined by polarization measurements in 3.5 wt.% NaCl solution. Spectroscopic analysis identified the formation of a chemical interaction between the NHC monolayer and the polymer film. The strong anchoring of NHC to iron along with its chemical interaction with the polymer film induced high stability and durability of the dual-layer coating to effectively protect the coated iron from corrosion formation.