Benzofluorene (C17H12) cations have been studied in the vapor phase by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The identification of certain fragmented species from electron impact/matrix optical experiments (see Banisaukas, J.; Szczepanski, J.; Vala, M.; Hirata, S. J. Phys. Chem. A 2004, 108 3713) provided the background for the present detailed studies of the dissociation pathways of the cation via FT-ICR mass spectrometry. Both hydrogen and acetylene loss pathways along various photodissociation routes have been identified.