Non-covalently crosslinked elastomers based on metal–ligand complexations have been comprehensively reported as functional materials, yet the coordination systems have been mostly built using nitrogen-containing aromatic ligands and transition metal ions. Inspired by the diverse nature of metal–ligand complexations, herein we report a novel network that, to the best of our knowledge, for the first time uses main-group aluminum ions to crosslink carboxyl-modified polysiloxanes [Al(III)-CPDMS]. The Al(III)-carboxylate complexation has been revealed to be effective in constructing an elastic network with self-healing and reprocessing properties. The mechanical and self-healing properties of Al(III)-CPDMS can be regulated by changing its chain length, carboxyl grafting density and Al(III) feed. We intend to present a design concept that facilely uses versatile coordination bonds to create novel functional elastic systems.