A series of poly(amino (meth)acrylate) brushes, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA), poly(2-(dimethylamino)ethyl acrylate) (PDMAEA), poly(2-(tert-butyl-amino)ethyl methacrylate) (PTBAEMA), has been synthesized via surface-confined controlled/living radical polymerizations using surface-confined initiator from silane self-assembled monolayers (SAMS) on silicon (Si) wafer substrates. Chemical methods and efficacies for two types of living radical polymerization, atom transfer radical (ATRP) and single electron transfer (SET-LRP), are described and contrasted for the surface confined polymerization of poly(amino (meth)acrylate)s. Effects of solvent, catalyst/ligand system, and temperature on polymerization success were examined. Chemical compositions after each reaction step were characterized with FTIR spectroscopy, contact angle goniometry, and X-ray photoelectron spectroscopy while the SAM and polymer brush thicknesses were measured with spectroscopic ellipsometry. For the first time, this study demonstrates successful surface-confined polymerization of a series of poly(amine (meth)acrylate) brushes from Si-SAM substrates using a copper metal electron donor catalyst. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6552-6560, 2009