This article describes a new class of self-healing materials formed by the copolymerization of ethylene and anisyl-substituted propylenes using a sterically demanding half-sandwich scandium catalyst. The copolymerization proceeded in a controlled fashion, affording unique multi-block copolymers composed of relatively long alternating ethylene-alt-anisylpropylene sequences and short ethylene−ethylene units. By controlling the molecular weight and varying the anisyl substituents, a series of copolymers that show a wide range of glass-transition temperatures (T_g) and mechanical properties have been obtained. The copolymers with T_g below room temperature showed remarkable self-healability, being able to autonomously self-heal upon mechanical damage not only in a dry environment but also in water and aqueous acid and alkaline solutions, while those with T_g around or above room temperature exhibited excellent shape-memory property. The unique mechanical properties may be ascribed to the phase separation of the crystalline ethylene−ethylene nanodomains from the ethylene-alt-anisylpropylene matrix.