We have developed a method for the arylation of nitronyl nitroxide without using its transition metal complex as a nucleophile. Various nitronyl nitroxide-substituted π-electronic compounds can be obtained from the parent nitronyl nitroxide and the corresponding aryl iodides using a combination of zero-valent palladium catalysts and a 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl ligand in the presence of sodium tert-butoxide. The utility of the method has been demonstrated by the direct synthesis of open-shell compounds with giant π-electronic systems, such as 10P.