Microcapsule-based self-healing coatings are currently a focal point in the field of corrosion-resistant coating due to their exceptional corrosion resistance and self-healing properties. In this study, 2,5-dimercapto-1,3,4-thiadiazole (DMTD), a corrosion inhibitor, was employed as core material, and hollow mesoporous silica nanoparticles (HMSNs) were used as shell material to prepare DMTD@HMSNs microcapsules through sol-gel and vacuum impregnation method. The influence of the alcohol-to-water ratio on the morphology of HMSNs was investigated. Additionally, the morphology, chemical structure of and core content of the microcapsules were analyzed by SEM, FT-IR, and TG. The experimental results demonstrate that the best morphology of HMSNs microspheres is obtained when the alcohol-to-water ratio is 9:1. It is confirmed that HMSNs can effectively load DMTD, with a loading rate of 25.38%. The corrosion resistance of epoxy (EP) composite coating with varying contents of DMTD@HMSNs microcapsules was investigated through saltwater immersion test and electrochemical impedance spectroscopy (EIS) experiment. The EP coating containing 5%DMTD@HMSNs microcapsules exhibits outstanding corrosion resistance and self-healing properties, the self-healing and corrosion inhibition mechanism was revealed.