Poly(4＇-vinylhexaphenylbenzene) is a new, readily soluble polymer with hexaphenylbenzene side groups. The hexaphenylbenzene moieties can be cyclodehydrogenated oxidatively with CuCl2/AlCl3 yielding hexa-peri-hexabenzocoronene units and resulting in linked polycyclic aromatic hydrocarbons (PAHs). The synthesis of copolymers with methyl methacrylate (MMA) or styrene is also possible. Cyclodehydrogenation of the MMA copolymer leads to a partially soluble material, which can be characterized by UV/vis spectroscopy.