Abstract: A combination of photopolymerization and emulsion templating method was used to prepare pH-responsive porous microspheres (8-HQ@pTM-DM) loaded with a corrosion sensing probe 8-hydroxyquinoline (8-HQ) in one step by introducing a pH-responsive monomer, dimethylaminoethyl methacrylate (DMAEMA). The effects of the addition of DMAEMA on the morphology and the release behavior of the porous microspheres were systematically investigated, and the effects of the pH-responsive microspheres on the coating warning performance and corrosion resistance were also examined. Results showed that the prepared porous microspheres 8-HQ@pTM-DM were pH-responsive, with the fastest release rate in acidic conditions. Functional coatings with corrosion warning and anti-corrosion properties were constructed by incorporating 8-HQ@pTM-DM into the resin, and the prepared coatings were responsive to Al³⁺ and could be used for early warning of corrosion of aluminum alloy substrates. The coating prepared with 8-HQ@pTM-DM microspheres showed a significant fluorescence warning effect on scratches, and the fluorescence intensity was more pronounced and the contrast and sensitivity were higher compared with that of the coating with non-responsive porous microspheres (8-HQ@pTMPTA). Meanwhile, due to the corrosion inhibitory effect of 8-HQ, the incorporation of 8-HQ@pTM-DM also improved the corrosion resistance of the coating.