Organoboron chemistry has been widely explored and developed in synthetic chemistry for over half a century and provides various elegant synthetic protocols in polymer synthesis. Compared with most trivalent bare organoboron compounds, N-coordinated organoboron shows better performances, such as air and moisture stability. This review summarizes the application of various N-coordinated boranes and boronic acid/esters in polymer synthesis and materials science. We introduce the significance of N-coordinated boranes and boronate esters for controllable polymer synthesis and systematically summarize the structures and properties of polymers containing N-coordinated boronate esters. Furthermore, we highlight the effect of N→B dative bonds on improving the performance of self-healing materials. We hope that, through this review, more researchers will realize the advantages of N-coordinated organoboron and promote the development of this direction in polymer synthesis and materials science.