The continuous development and optimization of the pioneered living anionic polymerization and the derived controlled/“living” polymerization mechanisms, as well as efficient modification/coupling methods, have greatly facilitated the preparation of complex copolymers. These complex copolymers with defined compositions and structures provided the models for theoretical research and advanced materials. Meanwhile, the controlled/“living” polymerization mechanisms have also greatly prompted the development of self-assembly technology, such as the polymerization-induced self-assembly (PISA) or modification-induced self-assembly (MISA) technique. The constructed nano-objects with diverse morphologies and functions served as the prototype for advanced nanomaterials. Generally, the controlled/“living” polymerization and the constructed copolymers or nano-objects are playing more and more, irreplaceable importance in the upcoming new technical revolution era.