A new multiblock copolymer self‐healing strategy is reported that centers on the synthesis of block copolymers designed with different self‐healing motifs incorporated into individual blocks. As a proof of concept, a novel pentablock copolymer (ABCBA) consisting of a poly(ethylene glycol) middle block and self‐healable symmetric blocks of a polymethacrylate with pendant disulfide linkages and carboxylic acids is synthesized by a combination of consecutive controlled radical polymerization with hydrolytic cleavage. Disulfide exchange reactions of pendant disulfide linkages and metal–ligand interactions of pendant carboxylic acids with ferric ions allow for the formation of dual crosslinked networks with dynamic disulfide and supramolecular crosslinkages. The resultant networks possessing self‐healing viscoelasticity enable self‐healing on macroscale damages through supramolecular metal–ligand interactions and disulfide exchange reactions at room or moderate temperatures. These preliminary results suggest that the strategy can offer the versatility in the development of multifunctional self‐healable materials in dual or multiple self‐healable mechanisms.