With the development of controlled polymerisation, almost all polymerisation strategies have been successfully transplanted to surface-initiated polymerisation. The resulting polymer brushes have emerged as an effective tool for surface functionalization and modulation of the surface properties of materials. To meet various demands it is possible to tailor a material surface with polymer brushes that have diverse dimensionalities, morphologies and compositions. The crowded environment within polymer brushes as well as the stretched conformation of polymer chains sometimes provide unique physicochemical properties, which lead to the delicate creation of inorganic-organic hybridised nanostructures, anti-fouling coatings, biomedical carriers, and materials for use in lubrication, photonics and energy storage. So far, challenges remain in the high-precision synthesis and topological control needed to realize extended applications of polymer brushes. In this Feature Article, we highlight the topology, potential application prospects and various synthetic protocols, particularly for recently established methods, for the efficient synthesis of polymer brushes, as well as their benefits and limitations.