A facile synthetic approach of conjugated rod-coil block copolymers with poly(para-phenylene) as the rod block and polystyrene or polyethylene glycol as the coil block was developed. The block copolymers were synthesized through a TEMPO-mediated radical polymerization of 3,5-cyclohexadiene-1,2-diol-derived monomers (diacetate, dibenzonate, and dicarbonate), followed by thermal aromatization of the polymer precursor. The living character of the polymerization and the structure of the copolymers were studied by NMR, GPC, TGA, and UV-vis spectroscopy. The average conjugation lengths of the copolymers were calculated according to their maxima in LTV-vis spectroscopy. (c) 2007 Wiley Periodicals, Inc.