Abstract This paper reports an investigation of photochemical cyclodehydrogenation for the preparation of polycyclic azaarenes. Various naphthoquinolines and naphthoisoquinolines were obtained from 2-, 3-, and 4-[2-(1-and 2-naphthyl) vinyl] pyridine. 4-[2-(3-Phenanthryl) vinyl] pyridine gave pyreno [1, 10-hij] isoquinoline. An efficient preparation of (2-arylvinyl) pyridines is described.