Thioether-based acrylate block polymers are conveniently prepared via reversible addition-fragmentation chain-transfer polymerization, and further combined with the merit of reversible metal-thioether coordination to fabricate a new type of smart thermoplastic materials. This metal/polymer hybrid architecture imparts extraordinary mechanical performance to the product materials, exhibiting an excellent ductility (breaking strain approximate to 1000%) as well as a relatively high breaking stress (1-5 MPa). Notably, it is facile to thermally process these materials into desired shapes (e.g., dog-bone specimens, films, disks, etc.). Most importantly, these thermoplastic materials are endowed with the smart characteristic of being self-healable under ambient conditions. To the authors' knowledge, it is the first report on thermally processable, self-healing, and mechanically tough thermoplastic materials based on thioether polymers. These discoveries not only provide a pioneering route to design and construct self-healing thermoplastics, but also elucidate the pathway toward a large portfolio of new hybrid materials built on the platform of organosulfur chemistry.