Alkoxyamine derivatives based on 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), N-tert-butyl-N-(1-diethylphosphono-(2,2-dimethylpropyl)) nitroxide (SG1) and N-tert-butyl-N-(2-methyl-1-phenylpropyl) nitroxide (TIPNO) containing a C-11 hydrophobic spacer and a reactive triethoxysilyl polar head, were synthesized and anchored to silicon wafers by the Langmuir-Blodgett reactive deposition technique at surface pressures ranging from 15 to 32 mN/m. Polystyrene brushes (M-n similar to 8500-66,400 g/mol) were grown from the alkoxyamine functionalized silicon wafers by nitroxide mediated radical polymerization and characterized by ellipsometry and water contact angle measurements. The main parameters influencing the grafting density and the degree of stretching of the brushes are the nitroxide polarity and, therefore, the behavior of the corresponding alkoxyamines at the air/water interface of the Langmuir-Blodgett trough. Depending on the alkoxyamine chemical structure and the surface pressure during Langmuir-Blodgett deposition, polystyrene brushes with grafting densities of 0.3-1.0 chains/nm(2) and stretching values of 40-70% were obtained. Regarding alkoxyamines deposited at high surface pressures, size exclusion chromatography experiments performed on both cleaved polystyrene brushes and chains simultaneously grown in the bulk revealed that the polymerization degree of the bulk and surface chains are significantly different, suggesting that steric constrains affect the polymerization kinetics occurring at the silicon surface. (C) 2008 Wiley Periodicals, Inc.