This report describes the remarkably rapid synthesis of polymer brushes under mild conditions (50 degrees C) using surface-initiated polymerization. The highly active atom transfer radical polymerization catalyst Cu(I)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane allows synthesis of 100 nm thick poly(tert-butyl acrylate) brushes from initiator-modified Au surfaces in just 5 min. Using the same catalyst, polymerization of 2-hydroxyethyl methacrylate and methyl methacrylate yielded 100 nm thick films in 10 and 60 min, respectively. Such growth rates are an order of magnitude greater than those for traditional free-radical polymerizations initiated from surfaces. These polymerizations also retain some features of controlled radical polymerizations, such as the ability to form block copolymer brushes.