In the present Feature Article, a kinetic strategy for controlling the microstructure of synthetic polymer chains prepared via a radical chain-growth polymerization process is presented. This approach was recently developed in our laboratory and relies on the controlled kinetic addition of ultrareactive N-substituted maleimides during the atom transfer radical polymerization of styrene. This method is experimentally straightforward and can be applied to a broad library of functional N-substituted maleimides. Thus, this platform allows synthesis of unprecedented polymer materials such as 1D macromolecular arrays. The basic kinetic requirements, the experimental conditions, and the synthetic scope of this approach are discussed in details herein.