Herein, halloysite nanotubes (HNTs) as typical micro-nano carrier were alkali etched to expand their aperture, then, on their surface 2-mercaptobenzothiazole (MBT) was deposited, and finally chitosan-polyethylene glycol copolymer (CP) was coated as top surface layer, thus a new filler of surface modified HNTs was made. Next, a novel self-healing coating (CP-HNTs-MBT) is developed with polydimethylsiloxane (PDMS) as matrix and the surface modified HNTs as filler etc., and then the coating is applied on Cu substrate. The structure and composition of the filler and the corrosion performance, especially its re-healing capacity in 3.5% NaCl solution of the coating are assessed via Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), UV absorption spectroscopy, immersion test, and Kelvin probe etc. Results indicate that MBT is successfully loaded onto HNTs, achieving a loading capacity of 12% by mass. The results of SEM, EIS, Kelvin probe, and UV absorption spectroscopy confirm the excellent self-healing performance of the CP-HNTs-MBT coating, which can still show significant self-healing ability, even when it is used for second time. It follows that the CP-HNTs-MBT coating exhibits strong corrosion resistance, with the ability to maintain self-healing ability for multiple cycle usage, thereby providing effective protection for metal materials.