AbstractHerein, we report the synthesis, crystal structure, and optical properties of a heterotriptycene consisting of an unsubstituted bispyrrole, 2,4,6,8‐tetrahydro‐4,8‐benzobenzo[1,2‐c:4,5‐c′]dipyrrole, which was synthesized via hetero‐Diels‐Alder reaction of a novel benzobicyclo[2.2.2]octane derivative. The compound formed a 2D nested hexagonal array with NH⋅⋅⋅π interactions in the crystalline state; whereas, in the solution state, it exhibited through‐space intramolecular charge transfer (ICT) induced emission in the solution state.