This paper describes a new way to synthesize rod-coil block copolymers consisting of poly(p-phenylene) (PPP) as rigid rod and either polystyrene (PS) or poly(ethylene oxide) (PEO) as flexible coil. The Suzuki-coupling of the AB-type monomer 4-bromo-2,5-diheptylbenzeneboronic acid (1) under strictly proton-free conditions leads to the control of PPP endgroups and hence allows the synthesis of a variety of differently end-functionalized poly(p-phenylene)s. The poly(2,5-diheptyl-p-phenylene)-block-polystyrene (7) is then prepared via condensation of anionically polymerized living polystyrene (6) with alpha-(4-formylphenyl)-omega-phenyl-poly(2,5diheptyl-p-phenylene) (4). Toluenesulfonic acid catalyzed condensation of alpha-methyl-omega-amino-poly(oxyethylene) (8) with PPP4 yields poly(2,5-diheptyl-p-phenylene)-block-poly(ethylene oxide) (9).