Ceramic coatings often suffer from the formation and expansion of microcracks, which leads to a failure of the protective function. In this work, we observed self-healing of the microcracks in the TiSiN/Ag multilayer coating upon heating. This behavior can be attributed to diffusion of the Ag atoms to the cracks in the multilayer coating, while similar cracks in the TiSiN monolayer coating remain unchanged after the same treatment. Furthermore, the TiSiN/Ag coating with healed cracks possesses similar electrochemical corrosion and biofouling properties to the as-deposited one, suggesting that TiSiN/Ag is a promising system in marine engineering applications. The mechanism of self-healing was explained by kinetic simulations based on ab initio molecular dynamics and the diffusion activation energies of Ag in irregular ceramic structures have been calculated. The here adopted theoretical method also provides a new pathway for exploring new coating systems with a potential self-healing function.