Active anticorrosive organic coatings adopting microcapsules (MCs) have lately attracted extensive attention as they were proven to be effective to minimize metal corrosions and offer a long-lasting protection performance. Herein, a novel environmental-friendly active corrosion protection system was designed for aluminum alloy 2024 (AA2024) based on water-based polyurethane coatings with the addition of water and alkaline pHresponsive smart MCs, which is fabricated by utilizing 2mercaptobenzothiazole (2-MBT) as an inhibitor, halloysite clay nanotubes (HNTs) as an inhibitor carrier, and the natural polyelectrolytes ε-poly-L-lysine (ε-PLL) and sodium alginate (SA) as layer-by-layer (LBL) encapsulation polyelectrolytes. Salt spray tests and electrochemical measurements prove that the scratched coatings with embedded MCs possess an excellent self-healing performance by forming an adsorption layer of released 2-MBT on the AA2024 surface, thereby providing over 90% inhibition efficiency within 6 days' immersion. The UV−vis spectrophotometer results further showed that the release of 2-MBT is a three-stage long-term process sensitive to water and alkaline pH value, while the outward release rate is both regulated by the solubility of 2-MBT and the SA layer. The fabricated MCs not only offer a great promise to provide an excellent self-healing performance but also shed light on the future design of advanced MCs on demand based on the LBL technique.