Aggregation-induced emission (AIE) materials have been used for non-destructive visual detection of cracks and damages to prevent the final structural failure and increase the service life of coatings. In this study, a self-warning and self-healing core–shell fiber is synthesized for developing AIE composite coatings. In these core–shell fibers, a mixture of hmethylene diisocyanate (HDI) and tetraphenylethylene (TPE) is used as core constituent, and polyacrylonitrile (PAN) is used for preparing the shell, which are continuously wrapped with a high loading rate through coaxial electrospinning technology. The parameters of electrospinning process are optimized to achieve core–shell fibers with smooth surface and average diameter of 100 ± 50 nm. The composite coating reveals effective fluorescence in case of cracks in a corrosive environment. The maximum self-healing efficiency of the fiber coating is 94.8 % after soaking for 120 h. The introduced composite coating paves the way for improving the safety and reliability of critical engineering components.