Synthesis of a polystyrene (PSt) grafted polyarylene with naphthalene groups in the main chain is described, 1,4-Dibromo-2,5-bis(bromomethyl)benzene was used as initiator in ATRP of styrene using CuBr/2,2'-bipyridine as catalyst and polymeric precursor, that possesses a designed molecular weight with a narrow molecular weight distribution and two bromine atoms directly linked to a central benzene ring, was obtained. The Suzuki coupling : between the bromine functionalized PSt and 1-naphthyl boronic acid furnished a macromonomer with naphthyl moieties as oxidable groups. Following chemical oxidative polymerization in the presence of anhydrous FeCl3, a soluble and processable polyarylene with PSt side chains was synthesized. The starting macromonomers as well as the final polyarylenes were analyzed by GPC and spectral methods (H-1-NMR, IR and UV-vis). The thermal behaviour of the polymers was studied by differential scanning calorimetry (DSC) and thermogravimetrical analysis (TGA).