Advances in controlled radical polymerization over the past two decades have transformed the ability to produce molecularly well-defined, chain-end tethered polymer brush films. The assets of controlled radical polymerization reactions have impacted the synthesis and properties of surface-grafted polymer brushes in various ways. This review article will highlight two aspects related to the preparation and use of polymer brush film that have benefited from these advances. The first part of this review will illustrate how surface-initiated controlled radical polymerization chemistries have allowed access to surface-grafted polymers with complex topologies. The second part of this article will discuss the use of surface-initiated controlled radical polymerization to prepare polymer brush-nanoparticle hybrid films. (C) 2019 Elsevier B.V. All rights reserved.