The mussel-inspired properties of dopamine have attracted immense scientific interest for surface modification of nanoparticles due to the high potential of dopamine functional groups to increase the adhesion of nanoparticles to flat surfaces. Here, we report for the first time a novel type of inhibitor-loaded nanocontainer using polydopamine (PDA) as a pH-sensitive gatekeeper for mesoporous silica nanoparticles (MSNs). The encapsulated inhibitor (benzotriazole) was loaded into MSNs at neutral pH, demonstrating fast release in an acidic environment. The self-healing effect of water-borne alkyd coatings doped with nanocontainers was achieved by both on-demand release of benzotriazole during the corrosion process and formation of the complexes between the dopamine functional groups and iron oxides, thus providing dual self-healing protection for the mild steel substrate. The coatings were characterized by electrochemical impedance spectroscopy, visual observations, and confocal Raman microscopy. In all cases, the coatings with embedded benzotriazole-loaded MSNs with PDA-decorated outer surfaces demonstrated superior self-healing effects on the damaged areas. We anticipate that dopamine-based multifunctional gatekeepers can find application potential not only in intelligent self-healing anticorrosive coatings but also in drug delivery, antimicrobial protection, and other fields.