Perchloroacenaphthylene(C12Cl8), a perchlorinated polycyclic hydrocarbon composed of two hexagons and a pentagon, was ablated by a pulsed laser beam in a vacuum. The products created from the laser ablation were characterized by high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry and rapid-scan ultraviolet spectrophotometric detection. Buckminsterfullerene C-60 and various perchlorinated carbon clusters have been observed among the products. The observation is helpful for understanding the formation mechanisms of fullerenes and suggests that the Pentagon Road scheme is feasible with the involvement of chlorines.