Amphiphilic A(3)B mikto-arm copolymers have been synthesized using a t-butyl-diphenyl silyl-based methylglucoside derivative. The latter has been first used as initiator for the polymerization of epsilon-caprolactone leading to three-arm star-shaped structures followed by several postpolymerization steps to obtain star-shaped poly(epsilon-caprolactone) macroinitiator. Atom transfer radical polymerization (ATRP) of diisopropylidene galactose methacrylate in THF at 60 degrees C using CuBr ligated with 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as catalytic complex allowed the formation of A(3)B mikto-arm copolymers with different compositions and molecular weights. Selective deprotection of sugar protecting groups finally generated amphiphilic mikto-arm copolymers. The molecular characterization of those copolymers was performed by H-1 NMR spectroscopy and gel permeation chromatography (GPC) analysis. The self-assembly of the copolymers into micellar aggregates and the related critical micellization concentration (CMC) in aqueous media were determined by dynamic light scattering (DLS) and UV-visible spectroscopy, respectively. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3271-3280, 2010