Well-defined omega-cholesteryl poly(n-hexyl isocyanate) (PHIC-Chol), as well as diblock copolymers of n-hexyl isocyanate (HIC) with styrene, PS-b-PHIC [PS = polystyrene; PHIC = poly(n-hexyl isocyanate)], and triblock terpolymers with styrene and isoprene, PS-b-PI-b-PHIC and PI-b-PS-b-PHIC (PI = polyisoprene), were synthesized with CpTiCl2(OR) (R = cholesteryl group, PS, or PS-b-PI) complexes. The synthetic strategy involved the reaction of the precursor complex CpTiCl3 with cholesterol or the suitable omega-hydroxy homopolymer or block copolymer, followed by the polymerization of HIC. The omega-hydroxy polymers were prepared by the anionic polymerization of the corresponding monomers and the reaction of the living chains with ethylene oxide. The reaction sequence was monitored by size exclusion chromatography, and the final products were characterized by size exclusion chromatography (light scattering and refractive-index detectors), nuclear magnetic resonance spectroscopy, and, in the case of PHIC-Chol, differential scanning calorimetry. (c) 2005 Wiley Periodicals, Inc.