The synthesis of an unprecedented, π‐extended hexabenzocorene (HBC)‐based diazahelicene is presented. The target compound was synthesized by an ortho‐fusion of two naphthalene diimide (NDI) units to a HBC‐skeleton. A combination of Diels–Alder and Scholl‐type oxidation reactions involving a symmetric di‐NDI‐tolane precursor were crucial for the very selective formation of the helical superstructure via a hexaphenyl‐benzene (HPB) derivative. The formation of the diazahelicene moiety in the final Scholl oxidation is favoured, affording the symmetric π‐extended helicene as the major product as a pair of enantiomers. The separation of the enantiomers was successfully accomplished by HPLC involving a chiral stationary phase. The absolute configuration of the enantiomers was assigned by comparison of circular dichroism spectra with quantum mechanical calculations.