[7]Helicenesfused with 3,3,4,4,5,5‐hexafluorocyclopentene (HFCP) have been synthesized by using oxidative photocyclization of stilbene derivatives, i.e., Mallory reaction. A novel double helicene compound featuring [4]‐ and [6]‐helicene motifs connected by sharing a peripheral benzene ring was also obtained. Optical properties including chiroptical character (CD and CPL properties) are described.