A noble approach based on the encapsulation of corrosion inhibitors has been presented, which are capable of improving the active corrosion protection without negatively influencing the barrier properties of the coating layers. Polymeric nanocapsules loaded with six types of amine corrosion inhibitors were synthesized by multi-stage emulsion polymerization. Depending on the basicity and water solubility of amines, different amounts of releasable corrosion inhibitors were encapsulated into the polymer capsules. Encapsulated organic amines were generally well released under alkaline conditions, and linear amines were more easily released from inside capsules than branched ones. The nanocapsules were incorporated into the coating resin and were coated on cold-rolled steel sheets to investigate corrosion protection efficiencies. The corrosion inhibitive efficiencies of the nanocapsule-containing coating layers were evaluated by electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET). In this study, it was revealed that the intrinsic properties of the amines as well as their encapsulation/release behaviors determined the barrier property and self-healing protection capability of the coating layer.