Polymer brushes have received great attention in recent years due to their distinctive properties and wide range of applications. The synthesis of polymer brushes typically employs surface-initiated atom transfer radical polymerization (SI-ATRP) techniques. To realize the control of the polymerization process in different environments, various SI-ATRP techniques triggered by different stimuli have been developed. This review focuses on the latest developments in different stimuli-triggered SI-ATRP methods, such as electrochemically mediated, photoinduced, enzyme-assisted, mechanically controlled, and organocatalyzed ATRP. Additionally, SI-ATRP technology triggered by a combination of multiple stimuli sources is also discussed. Furthermore, the applications of polymer brushes in lubrication, biological applications, antifouling, and catalysis are also systematically summarized and discussed. Despite the advancements in the synthesis of various types of 1D, 2D, and 3D polymer brushes via controlled radical polymerization, contemporary challenges remain in the quest for more efficient and straightforward synthetic protocols that allow for precise control over the composition, structure, and functionality of polymer brushes. We anticipate the readers could promote the understanding of surface functionalization based on ATRP-mediated polymer brushes and envision future directions for their application in surface coating technologies.