Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free-radical copolymerization of methacryloyl-terminated PS and α-vinylbenzyl-ω-hydroxy or α-vinylbenzyl-ω-perfluoroalkyl (Rf) PEO macromonomers with the addition of Lewis acid (SnCl4). It was found from their dilute-solution properties that PS/PEO end-capped with Rf (PBRf), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N-dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBRf-type brush by chemical modification, using corresponding acid chloride. The substitution of Rf groups was ∼70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006