This article describes that glucose, maltose, maltotriose, maltotetraose, maltopentaose, and maltohexaose (a, b, c, d, e, and f, respectively) were introduced into the initiating chain-end of polystyrene (PSt) through the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated radical polymerization. A series of glycoconjuaged. TEMPO-adducts, 1a-f, was synthesized and used as the initiators for the polymerization of styrene (St) for 6 h at 120 degrees C to afford the end-functionalized PSt's with the acetyl saccharides, 2a-f, in the yields of 37-43%. For 2a-f obtained by the polymerizations using the [St]/[1] of 125, 250, and 500, the number-average molecular weights determined by size exclusion chromatography (SEC), M-n,M-SEC's, were 4800-6300, 8800-10,600, and 18,40025,200, respectively, which fairly agreed with the predicted values. The end-functionalized PSt's with saccharides, 3a-f, which were obtained from the deacetylation of 2a-f using sodium metboxide in dry THF, formed the polymeric reverse micelles consisting of a saccharide-core and a PSt-shell in chloroform and toluene. The static laser light scattering (SLS) measurements provided the average molar mass of the aggregates in toluene, M-w,M-SLS's, which ranged from 7.50 x 10(4) to 1.77 x 10(5) for 3a, from 1.90 x 10(5) to 4.93 x 10(5) for 3b, from 4.41 x 10(5) to 7.21 x 10(5) for 3c, from 5.85 x 10(5) to 8.51 x 10(5) for 3d, from 7.55 x 10(5) to 8.53 x 10(5) for 3e, and from 8.54 x 10(5) to 9.26 x 10(5) for 3f The aggregation numbers, N-agg's, which were calculated from the M-w,(SLS)'s, were from 7 to 24 for 3a, from 20 to 37 for 3b, from 34 to 89 for 3c, from 39 to 116 for 3d, from 41 to 145 for 3e and from 31 to 146 for 3f It was confirmed that the aggregation property, such as the M-w,M-SLS or N-agg values, was strongly related to the polymerization degrees of St (DP's) or the number of the glucose residues (n's) for 3a-f. (c) 2006 Wiley Periodicals, Inc.