Maltopentaose (Mal(5))-conjugated surface-active styrenic monomers 1a, 1b, and 1c are described, which contain hydrophobic spacers, such as C1, C5, and C7 alkylene chains, respectively. The glycomonomers 1a-c were synthesized by the direct -N-glycosyl reaction of styrene derivatives with aminoalkyl groups 4a-c onto Mal(5) in dry methanol, followed by the N-acetylation with acetic anhydride. The self-assembling properties for the aqueous solutions of 1a-c were characterized by surface tension measurements and light scattering experiments, providing the physicochemical parameters for the formed 1a-c micelles including the critical micelle concentration, apparent hydrodynamic radius (R-h,R-app), and weight average aggregation number (N-agg). The transmission electron microscope observations revealed the most important result in this study that 1a produced loose spherical micelles with the number average diameter (d(n)) of 26 nm, while both 1b and 1c formed worm-like micelles with the polymerizable core and the Mal(5) shell, whose number average contour lengths (l(n)s) were 130 nm and 68 nm, respectively. The radical homopolymerizations of 1a-c in water provided a substantial result in this study that 1b and 1c, that is, the glycomonomers forming the worm-like micelles, showed a very high homopolymerizability in water. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1671-1679