A novel doubly cyclopentannulated carbazole which is accessible through a successive π‐expansion of di(1‐naphthylamine) is disclosed. The carbazole moiety is generated in the final step through intramolecular oxidative coupling. The π‐expansion of carbazole resulted in strongly altered optoelectronic and electrochemical properties. The solid‐state structure features an interesting packing motif with alternating face‐to‐face π⋅⋅⋅π and edge‐to‐face C−H⋅⋅⋅π interactions. The experimental findings were corroborated by theoretical calculations.