We present the synthesis of reactive polymer brushes prepared by surface reversible additionfragmentation chain transfer polymerization of pentafluorophenyl acrylate. The reactive ester moieties can be used to functionalize the polymer brush film with virtually any functionality by simple post-polymerization modification with amines. Dithiobenzoic acid benzyl-(4-ethyltrimethoxylsilyl) ester was used as the surface chain transfer agent (S-CTA) and the anchoring group onto the silicon substrates. Reactive polymer brushes with adjustable molecular weight, high grafting density, and conformal coverage through the grafting-from approach were obtained. Subsequently, the reactive polymer brushes were converted with amino-spiropyrans resulting in reversible light-responsive polymer brush films. The wetting behavior could be altered by irradiation with ultraviolet (UV) or visible light. Furthermore, a patterned surface of polymer brushes was obtained using a lithography technique. UV irradiation of the S-CTA-modified substrates leads to a selective degradation of S-CTA in the exposed areas and gives patterned activated polymer brushes after a subsequent RAFT polymerization step. Conversion of the patterned polymer brushes with 5-((2-aminoethyl)amino)naphthalene-1-sulfonic acid resulted in patterned fluorescent polymer brush films. The utilization of reactive polymer brushes offers an easy approach in the fabrication of highly functional brushes, even for functionalities whose introduction is limited by other strategies. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012