The following block-comb/graft copolymers of styrene (S), isoprene (1), and butadiene (B)-PS-b-(PB-g-PB), PS-b-(PB-g-PB)-b-PS, (PB-g-PB)-b-P2VP, (PS-g-PB)-b-(PI-g-PS), (PS-g-PB)-b-(PI-g-PS)-b-(PB-g-PI), (PS-g-PB)-b-(PI-g-PS)-b-(PB-g-PI)b-(PI-g-PS)-b-(PS-g-PB), and (PS)2(PB-g-PB) [where PS is polystyrene, PB is polybutadiene, P2VP is poly(2-vinylpyridine) (2VP), and PI is polyisoprene]-were synthesized with the macromonomer strategy and anionic polymerization high-vacuum techniques. The synthetic approach involves the synthesis and block copolymerization of styrenic macromonomers in situ without isolation. The prepared samples were characterized by size exclusion chromatography with a differential refractometer detector, size exclusion chromatography with a two-angle laser light scattering detector, and NMR spectroscopy. (c) 2005 Wiley Periodicals, Inc.