In biological system, early detection and treatment at the same moment is highly required. For synthetic materials, it is demanding to develop materials that possess self-reporting of early damage and self-healing simultaneously. This dual function is achieved in this work by introducing an intelligent pH-responsive coatings based on poly(divinylbenzene)-graft-poly(divinylbenzene-co-methacrylic acid) (PDVB-graft-P(DVB-co-AA)) core-shell microspheres as smart components of the polymer coatings for corrosion protection. The key component, synthesized PDVB-graft-P(DVB-co-AA) core-shell microspheres are porous and pH responsive. The porosity allows for encapsulation of the corrosion inhibitor of benzotriazole and the fluorescent probe, coumarin. Both loading capacities can be up to about 15 wt%. The polymeric coatings doped with the synthesized microspheres can adapt immediately to the varied variation in pH value from the electrochemical corrosion reaction and release active molecules on demand onto the damaged cracks of the coatings on metal surfaces. It leads simultaneously to the dual functions of self-healing and self-reporting. The corrosion area can be self-reported in 6 h, while the substrate can be protected at least for 1 month in 3.5 wt% NaCl solution. These pH-responsive materials with self-reporting and self-healing dual functions are highly expected to have a bright future due to their smart, long-lasting, recyclable, and multifunctional properties.