We developed a very efficient and expandable divergent approach initiated by a direct electrophilic borylation at phenyl rings to synthesize a series of double heterohelicenes. Their π-extended structures with pristine zigzag nitrogen (N)-boron (B)-nitrogen (N) edges offer them substantial physical properties and strong double hydrogen-bond donating capability. The isolated (P,P) and (M,M) enantiomers exhibit circularly polarized luminescence in response to hydrogen-bonding interactions.