A self-healing product having a shape memory component and a healing component interpenetrating the shape memory component to form a fibrous microstructure. The healing component is selected so as to diffuse into a defect when the area of the product with the defect is subject to a treatment. The components may be selected so that applying heat at a temperature at or above a melting temperature (Tm) and/or a glass transition temperature (Tg) for one or both of the shape memory component and the healing component causes shape memory transition and diffusion by the healing component. The self-healing product can form a coating or material layer to protect a substrate while also providing the healing properties responsive to the treatment.