The synthesis of polymers is of academic value and technological implication and has been developed as an important area of research over a long history. 1 The first reports about “polymerization” reactions can be traced back to as early as the 19th century: in 1839, Simon observed that styrene changed from liquid to solid upon heating, while in 1872, Bayer recorded that the reactions of phenols with aldehydes resulted in the formation of resinous substances, 2, 3 although at that time people had no idea about what a “polymer” was. In the 1920s, Staudinger proposed the concept of “macromolecules”, and in the 1930s, Carothers succeeded in the syntheses of polyesters and worked out theoretical models for condensation polymerization. 4, 5 These seminal works in the early 20th century laid a solid foundation for polymer chemistry and changed polymer syntheses from arts or skills to real science. 1 In the modern textbook of polymer chemistry, polymerization reactions are generally categorized into two types: step and chain polymerizations, typical examples of which are condensation polymerization of difunctional monomers and addition polymerization of olefinic monomers, respectively. 1, 6-8 We now know that Bayer’s phenol-aldehyde reaction is a step polymerization and that Simon’s styrene reaction is a chain polymerization. Generally speaking, when molecules of a difunctional monomer such as XRY (where X and Y are mutually reactive functional groups) are polymerized via the elimination of small molecule byproducts of XY, a linear condensation polymer with a general formula of X-(-R-) n-Y is formed, while when molecules of an olefinic monomer such as H2CdCHR are polymerized, a vinyl polymer with a structure of-[-H2C-CH (R)-] n-is produced (Scheme 1). The difunctional and olefinic monomers have been the major monomer sources, and their step and chain polymerization reactions have been the main synthetic routes to the “conventional” polymers such as polyester and polystyrene (PS), respectively. From the viewpoint of bond structure, the step polymerization of the difunctional monomer and the chain polymerization of the vinyl monomer sketched in Scheme 1 are single-and double-bond reactions, respectively. When the single and double bonds of the monomeric species are opened and reacted, new species with higher molecular weights are formed. The final destinies of these chemical reactions are the formation of polymeric products, whose monomer repeat units are connected by single bonds. Since the single bonds are electronically saturated, these polymers are generally electronically inactive. As a result, traditional polymers are