In this article, supramolecular silicone elastomers with self-healing function were first prepared by simple and controllable salt-forming vulcanization of polyaminopropylmethylsiloxane with acids. Their structures and micrographs were verified by Fourier transform infrared spectra, Small-angle X-ray scattering experiments and atomic force microscope. The experimental results showed that the ion-association complexes were formed during vulcanization, and the obtained elastomers displayed self-healing and good mechanical properties even if the cross-linking agent was excessed. The thermogravimetric analysis showed that the elastomers crosslinked by inorganic acid were stable under high temperature. Unexpectedly, bionic structures were observed in the elastomers, which further changed the hydrophobicity of the surfaces of the elastomers physically. (c) 2017 Wiley Periodicals, Inc.