Combination of coordination polymerization and atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod-coil block copolymers. The procedure included the following steps: (1) monoesterification reaction of ethylene glycol with 2-bromoisobutyryl bromide yielded a alpha-bromo, omega-hydroxy bifunctional initiator, (2) CpTiCl3 (bifunctional initiator) catalyst was prepared from a mixture of trichlorocyclopentadienyl titanium (CpTiCl3) and bifunctional initiator. Coordination polymerization of n-butyl isocyanate initiated by such catalyst provided a well-defined macroinitiator, poly(n-butyl isocyanate)-Br (PBIC-Br), and (3) ATRP method of vinyl monomers using PBIC-Br provided rod (PBIC)-coil block copolymers. (C) 2007 Wiley Periodicals, Inc.